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  • 1995-1999  (1,845)
  • 1960-1964  (3,704)
  • 1920-1924  (3,032)
  • 1910-1914  (3,530)
  • Inorganic Chemistry  (12,038)
  • Phosphorus
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  • 1
    Electronic Resource
    Electronic Resource
    Mycorrhizal influence on protein and lipid of durum wheat grown at different soil phosphorus levels (1999)
    Springer
    Mycorrhiza 9 (1999), S. 97-101 
    Details
    ISSN: 1432-1890
    Keywords: Key words Glomus mosseae ; Lipid ; Phosphorus ; Protein ; Seed ; Triticum durum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  Root colonization by arbuscular mycorrhizal fungi (AMF) may affect protein and lipid composition of plants by altering P nutrition or by eliciting other metabolic responses in the host plant. This study was conducted to determine the effects of an AMF and soil P on seed protein and lipid contents and yield of two genotypes of durum wheat (Triticum durum L.). Plants were grown in a greenhouse using soil: sand mixes with different levels of P, and with or without the AMF Glomus mosseae [(Nicol. and Gerd.) Gerd. and Trappe]. Percentage AMF root colonization decreased as P added to soil increased. The wheat genotype CR057 had higher AMF root colonization but lower seed P and protein concentrations than CR006. Without added soil P, protein concentration was significantly lower and lipid concentration and seed dry weight higher in arbuscular mycorrhizal (AM) than in nonAM plants. Seed lipid and protein contents were highly correlated with P content of plants. In nonAM plants, seed lipid and protein contents were low with no added soil P and did not differ with added soil P. Seed protein/lipid (Pro/L) concentration ratios of AM plants were higher than those of nonAM plants only when no P was added to the soil. The data indicate different patterns of seed P accumulation and different relationships between seed P and protein and lipid in AM and nonAM plants. Thus, both the presence and degree of AMF root colonization affected seed lipid metabolism in these durum wheat genotypes.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s005720050006
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  • 2
    Electronic Resource
    Electronic Resource
    The mycorrhizal status of an emergent aquatic, Lythrum salicaria L., at different levels of phosphorus availability (1999)
    Springer
    Mycorrhiza 9 (1999), S. 191-197 
    Details
    ISSN: 1432-1890
    Keywords: Key words Arbuscular mycorrhizae ; Lythrumsalicaria ; Phosphorus ; Wetland ; Emergent aquatic
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The relationship between nutrient availability and mycorrhizal status has been well studied for terrestrial plant species, but has been examined rarely in aquatic and emergent aquatic species. The purpose of this study was to determine the effect of phosphorus availability on the arbuscular mycorrhizal (AM) status of an emergent aquatic, Lythrum salicaria L. L. salicaria was grown in hydroponic sand culture at five phosphorus concentrations (0, 100, 1000, 10 000, and 47 500 μg PO4/l nutrient solution) for 49 days with or without mycorrhizal inoculum obtained from wetland soil. Inoculated plants at the lowest three phosphorus concentrations were colonized by AM, whereas there was no colonization of plants grown at the highest two phosphorus concentrations. Colonization by AM fungi occurred in conjunction with symptoms of phosphorus deficiency in L. salicaria under experimental conditions: plants at the lowest three phosphorus concentrations had lower biomass and higher root: shoot weight ratios than plants at the highest two concentrations. However, total biomass and internal phosphorus concentration did not differ between inoculated and control plants. Further studies are needed under conditions more closely mimicking natural dynamics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s005720050266
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  • 3
    Electronic Resource
    Electronic Resource
    Pisolithus arhizus ectomycorrhiza affects plant competition for phosphorus between Pinus elliottii and Panicum chamaelonche (1999)
    Springer
    Mycorrhiza 9 (1999), S. 199-204 
    Details
    ISSN: 1432-1890
    Keywords: Key words Competition ; Ectomycorrhiza ; External hyphae ; Phosphorus ; Pisolithus arhizus ; Uptake kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  Our objective was to evaluate the ability of an ectomycorrhizal fungus to alter the competitive interaction of pine seedlings growing with grass, and to determine whether the interaction was modified by soil-phosphorus (P) concentration. Slash pine (Pinus elliottii), inoculated with the ectomycorrhizal fungus Pisolithus arhizus or fortuitously colonized by Thelephora terrestris, and a native grass (Panicum chamaelonche) were grown in a greenhouse at three P levels (0.32, 3.22, 32.26 μM H3PO4). Pine inoculated with P. arhizus took up more P when competing with the nonmycorrhizal grass than when competing with another pine (irrespective of pine mycorrhizal status). Phosphorus uptake kinetics (Cmin, the minimum concentration at which P can be absorbed from a solution; Imax, the maximum uptake rate) for pine and grass were also determined under hydroponic conditions. Pine had a higher Imax than grass but grass had a lower Cmin, suggesting that pine is more competitive at higher nutrient concentrations while grass is more competitive at lower nutrient concentrations. The controlled conditions used in these experiments allowed us to evaluate specific parameters (P uptake and absorbing surface area) affecting plant competition.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s005720050267
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  • 4
    Electronic Resource
    Electronic Resource
    Leucaena hedgerow intercropping and cattle manure application in the Ethiopian highlands III. Nutrient balances (1999)
    Springer
    Biology and fertility of soils 28 (1999), S. 204-211 
    Details
    ISSN: 1432-0789
    Keywords: Key words Alley cropping ; Calcium ; Magnesium ; Nitrogen ; Phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  Balances between nutrients applied or mineralized and nutrients removed in maize grain and stover were calculated in a hedgerow intercropping experiment in which Leucaena leucocephala and L. pallida prunings and cattle manure were applied. Hedgerow intercropping (also called alley cropping) is an agroforestry system in which trees are grown in dense hedges between alleys where short-cycle crops are grown. The hedges are pruned periodically during the cropping period and the prunings are added to the soil as green manure. In control treatments, nutrient depletion per season was in the order of 7–19 kg N ha–1, 4–12 kg P ha–1, 10–26 kg K ha–1, 0–2 kg Ca ha–1 and 3–6 kg Mg ha–1. N fertilizer reversed the depletion of N, but it accelerated the depletion of the other nutrients. Manure and at least two applications of leucaena prunings resulted in net positive balances of N, K, and Ca between amounts applied or mineralized and amounts removed by maize. The amounts of P and Mg applied with, or mineralized from, prunings or manure were insufficient to offset the negative balances of these nutrients.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s003740050484
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  • 5
    Electronic Resource
    Electronic Resource
    Leucaena hedgerow intercropping and cattle manure application in the Ethiopian highlands I. Decomposition and nutrient release (1999)
    Springer
    Biology and fertility of soils 28 (1999), S. 182-195 
    Details
    ISSN: 1432-0789
    Keywords: Key words Alley cropping ; Calcium ; Magnesium ; Nitrogen ; Phosphorus ; Intercropping
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  A litter bag technique was used to study the decomposition and release of N, P, K, Ca, and Mg from Leucaena leucocephala and L. pallida prunings and cattle manure in a hedgerow intercropping trial conducted in the Ethiopian highlands. Hedgerow intercropping (also called alley cropping or alley farming) is an agroforestry system in which trees are grown in dense hedges between alleys where short-cycle crops are grown. The hedges are pruned periodically during the cropping period and the prunings are added to the soil as green manure. Manure was the most resistant to decomposition, losing only 15% of its dry matter (DM) in 15 weeks, compared to 41–57% lost by leucaena prunings. Large quantities of K (up to 104 kg ha–1) were mineralized from prunings and manure, but Ca and Mg were mostly immobilized. More N and P were released from prunings than from manure, which resulted in net immobilization of these nutrients in the initial stages of decomposition and net mineralization in later stages. Between the leucaenas more N was mineralized and less Ca and Mg were immobilized when L. leucocephala prunings were applied than when L. pallida prunings were applied. Fertilizer N increased DM decomposition and N mineralization. Mineralization of the nutrients was constrained by lignin and polyphenol contents. It is concluded that leucaena mulch and cattle manure may be significant sources of N and K for crop growth, but external sources of P, Ca and Mg may be required, particularly in acid soils which have low contents of these nutrients. However, this fertility effect has to be evaluated against the competition effect of trees to predict crop response.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s003740050482
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  • 6
    Electronic Resource
    Electronic Resource
    Leucaena hedgerow intercropping and cattle manure application in the Ethiopian highlands II. Maize yields and nutrient uptake (1999)
    Springer
    Biology and fertility of soils 28 (1999), S. 196-203 
    Details
    ISSN: 1432-0789
    Keywords: Key words Alley cropping ; Calcium ; Magnesium ; Nitrogen ; Phosphorus ; Leaf pruning
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  The effects of Leucaena leucocephala and L. pallida prunings and cattle manure on maize nutrient uptake and yield were investigated in a hedgerow intercropping trial in the Ethiopian highlands. Hedgerow intercropping (also called alley cropping) is an agroforestry system in which trees are grown in dense hedges between alleys where short-cycle crops are grown. The hedges are pruned periodically during the cropping period and the prunings are added to the soil as green manure. For each leucaena species, the experiment had 16 treatments resulting from a factorial combination of four levels of leucaena leaf prunings (no prunings applied; first prunings applied; first and second prunings applied; first, second and third prunings applied), two levels of air-dried cattle manure (0 and 3 t dry matter ha–1) and two levels of N fertilizer (0 and 40 kg N ha–1 as urea). Uptake of N, P and K increased significantly with application of the three nutrient sources, but uptake of Ca and Mg either did not respond or decreased with application of prunings and manure. All the three factors increased maize grain and stover yields significantly, usually with no significant interactions between the factors. At least two applications of prunings were required to significantly increase nutrient uptake and maize yield. Maize in the row closest to the hedge did not respond to these nutrient inputs. It is concluded that hedgerow intercropping, with or without manure application, can increase crop yields moderately (to 2–3 t ha–1 maize grain yields) in the highlands, but P, Ca and Mg may have to be supplied from external sources if they are deficient in the soil. Additional N is still required for higher yields (〉4 t ha–1 maize grain yields). However, quantification of the competition effects of the trees is also required to confirm these results.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s003740050483
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  • 7
    Electronic Resource
    Electronic Resource
    Rainfall effects on erosion of earthworm casts and phosphorus transfers by water runoff (1999)
    Springer
    Biology and fertility of soils 30 (1999), S. 7-13 
    Details
    ISSN: 1432-0789
    Keywords: Key words Earthworm ; Surface casts ; Rainfall events ; Soil erosion ; Phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  We investigated whether, under a temperate climate and in a maize crop, earthworm casts could contribute to soil erosion and further favour the exportation of phosphorus by runoff waters. Recording of casts was made in compacted (wheel-tracks) and non-compacted inter-rows, for a 2-month period in spring. To assess the rainfall impact on cast evolution, half of the observation sites were protected against rain splash by a nylon mesh placed above the soil surface. The water runoff was collected and analysed for sediment contents and phosphorus concentration. The mean annual production of surface casts was calculated to be 34 kg (dry weight) year–1 kg–1 earthworm (fresh weight). Synchronization between cast erosion and rainfall events was shown under natural conditions (unprotected sites). The erosion rate was 4 times greater over rainy periods than dry ones, reaching 80% of cast numbers. It appeared that not the runoff effect but the splash effect, due to the kinetics of the drops, disrupted casts. Newly formed casts disappeared first, with the erosion rate decreasing twofold for casts more than 10 days old. Cast erosion and runoff, as well as worm casting activity, were greater under compacted sites than under non-compacted sites, indicating an influence of earthworms on soil erosion from compacted soils. The total phosphorus content was similar in casts and uningested soil (0.80 mg phosphorus g–1). Potential phosphorus losses from cast erosion was calculated to reach 25–49 mg phosphorus m–2 per rainfall event depending on soil compaction. The amounts of particulate phosphorus recovered in water runoff after each rainfall event varied from 1 mg to 11 mg phosphorus. These results are compared and discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s003740050580
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  • 8
    Electronic Resource
    Electronic Resource
    Nitrogen and phosphorus uptake in two Idaho (USA) headwater wilderness streams (1999)
    Springer
    Oecologia 119 (1999), S. 247-255 
    Details
    ISSN: 1432-1939
    Keywords: Key words Nitrogen ; Phosphorus ; Nutrient spiraling ; Uptake rate and length ; Stream nutrient cycling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Nitrate and phosphate solutions were released into two reaches of two central Idaho streams to determine within- and between-stream variability in uptake lengths, uptake rates, and mass transfer coefficients. Physical and biotic stream characteristics and periphyton nitrate-uptake rates in recirculating chambers were measured to determine their influence on nutrient dynamics. Phosphate uptake length did not differ among the four reaches. There were no within-stream differences in nitrate uptake lengths but they did differ between the two streams. Long nitrate uptake lengths likely were due to instream concentrations above saturation but also may have been influenced by differences in active surface area and algal abundance. Nitrate and phosphate uptake lengths were longer, and uptake rates higher, than most other published values. However, mass transfer coefficients were comparable to measurements in other streams. Mass transfer coefficients may be a better parameter for temporal and spatial comparisons of instream nutrient dynamics, and for determining the underlying causes of variability in uptake length.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004420050783
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  • 9
    Electronic Resource
    Electronic Resource
    Importance of epiphytic cyanobacteria as food sources for heterotrophs in a tropical seagrass bed (1999)
    Springer
    Coral reefs 18 (1999), S. 263-271 
    Details
    ISSN: 1432-0975
    Keywords: Key words Syringodium isoetifolium ; Cyanobacteria ; Stable isotopes ; Nitrogen ; Phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences
    Notes: Abstract  The natural carbon and nitrogen stable isotope ratios (δ13C, δ15N) of various autotrophs and heterotrophs were measured in a Syringodium isoetifolium-dominated seagrass bed at Dravuni Island, Fiji to define carbon and nitrogen sources for heterotrophic organisms in a system where few animals graze directly on seagrass leaves. The organic carbon, nitrogen, and phosphorus content of organisms was also determined. The δ13C and δ15N data suggest that herbivorous heterotrophs in this seagrass bed depend significantly on epiphytic cyanobacteria rather than seagrass leaves and its detritus. This can be attributed to relative differences in nitrogen content of those organic materials. The cyanobacteria nitrogen content (3.6–4.8% of DW) is nearly half that of heterotrophs (7.0–8.6% N of DW) while that of S. isoetifolium origin (0.6–1.1% N of DW) is less than one third of the cyanobacteria nitrogen content. Phosphorus content was similar among cyanobacteria (0.8–1.1 mg g-1) and S. isoetifolium (0.4–1.4 mg g-1). These results suggest that cyanobacteria are important food sources for heterotrophs at the study site, and that inorganic nitrogen released through breakdown of cyanobacteria by heterotrophs may support the continued production of S. isoetifolium.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s003380050191
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  • 10
    Electronic Resource
    Electronic Resource
    Modelling nutrient fluxes from source to river load: a macroscopic analysis applied to the Rhine and Elbe basins (1999)
    Springer
    Hydrobiologia 410 (1999), S. 123-130 
    Details
    ISSN: 1573-5117
    Keywords: Nitrogen ; Phosphorus ; rivers ; modelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract In many European rivers, including the major streams of the Rhine and Elbe basins, the nutrient load (N and P) still exceeds target levels. In this paper, a model is presented that describes the river nutrient load as a function of nutrient sources, runoff and lithology in the upstream basin. The model was tested with independent data on nutrient sources (input) and nutrient river load (output) for 130 specific combinations of sub-basins and 5 year periods. A wide range of river systems within the Rhine and Elbe basins were included and the analysis covers a period of 25 years from 1970 to 1995. Most of the observed spatial and temporal variation in the average annual river nutrient load was successfully described by the model. It is therefore concluded that the model can be used to predict the effect of changes in nutrient sources (e.g. reduction of livestock numbers, further improvement of waste water treatment plants etc.) on the average annual nutrient loads of the rivers Rhine, Elbe and their main tributaries.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1003783109031
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  • 11
    Electronic Resource
    Electronic Resource
    Insights into the Staudinger Reaction: Experimental and Theoretical Studies on the Stabilization of cis-Phosphazides (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 1659-1664 
    Details
    ISSN: 1434-1948
    Keywords: Phosphorus ; Iminophosphorane ; Staudinger reaction ; Heterocycles ; Ab initio calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Staudinger-model reaction H3P (1) + HN3 (2) → H3P=NH (5) + N2 (6) has been investigated at the CCSD(T)/6-31G**//MP2(Full)/6-31G* level. Primary products formed in this reaction are the phosphazides H3P=N-N=NH (3) which exist as trans and cis isomers. In contrast to some previous assumptions, cis -3is 8.2 kcal mol-1 more stable than trans -3 but decomposes rather easily into the expected products H3P=NH and N2. This decomposition can be effectively hampered by intramolecular donor-acceptor interactions as shown by calculations on model compounds as well as by experiments. Thus the reaction of a methylene-σ3,λ3-phosphanyl-σ5,λ5-phosphorane with PhN3 led to a new four-membered heterocycle containing a thermally remarkable stable cis-phosphazide moiety.
    Additional Material: 4 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    Formation of Calcium-Carbon Bonds From a Lewis Acid-Base Reaction of Calcium Bis[bis(trimethylsilyl)amide] and Tris(trimethylsilylmethyl)alane (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2209-2214 
    Details
    ISSN: 1434-1948
    Keywords: Aluminium ; Amides ; Calcium ; Metallacycles ; Phosphorus ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of calcium bis[bis(trimethylsilyl)amide] with two equivalents of tris(trimethylsilylmethyl)alane yields (Me3SiCH2)2Al-N(SiMe3)2 (1) and the dimer [(Me3Si)2N-Ca(μ-CH2SiMe3)2Al(CH2SiMe3)2]2 (2). The five-coordinate bridging carbon atoms show Ca-C bond lengths of 264 and 268 pm. A similar reaction with calcium bis[bis(trimethylsilyl)phosphanide] gives the dimer [(Me3SiCH2)2Al-P(SiMe3)2]2 (3) with crystallographic C2 symmetry. A calcium-containing species is not isolable, however, in the presence of DME - ether cleavage reactions and the formation of the centrosymmetric dimer [(Me3SiCH2)2Al-OCH2CH2OMe]2 (4) are observed. The central moiety is an Al2O2 cycle with fivefold coordinated aluminium centers.
    Additional Material: 4 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    Magnesiation of Triisopropylsilylphosphane: Synthesis and Structures of New Mg2nP2m Polyhedra (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2215-2220 
    Details
    ISSN: 1434-1948
    Keywords: Magnesium ; Metalation ; Phosphorus ; Polyhedra ; X-ray structures ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The magnesiation of triisopropylsilylphosphane with dibutylmagnesium in toluene yields the octanuclear complex [Mg8(PSiiPr3)6{P(H)SiiPr3}4] (1) which consists of MgPSiiPr3 units forming a hexagonal Mg6P6 prism, with two opposite Mg2P2 moieties capped by additional Mg[P(H)SiiPr3]2 groups. If a small amount of THF is present during the metalation reaction [(THF)4Mg6(PSiiPr3)6] (2) also containing a hexagonal Mg6P6 prism can be isolated. The magnesiation of H2P-SiiPr3 in tetrahydrofuran leads to the formation of the tetrameric complex [(THF)MgPSiiPr3]4(3) with a slightly distorted Mg4P4 cubane-like structure.The structures depend strongly on the steric strain caused by the trialkylsilyl substituents and the neutral coligands at the magnesium center. The highest steric strain, which is induced by coordination to every magnesium atom, leads to the smallest MgnPn polyhedron - the central Mg4P4 heterocubane moiety. In compounds 1 and 2 the hexagonal Mg6P6 prism is formed, however, with reduced steric strain as observed for 2 where the Mg-P bond lengths become more similar.
    Additional Material: 4 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    N-Thiophosphorylated and N-Phosphorylated Iminophosphoranes [R3P=N-P(X)R′2; × = O, S] as Models for Dendrimers: Synthesis, Reactivity and Crystal Structures (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 601-611 
    Details
    ISSN: 1434-1948
    Keywords: Phosphorus ; Ferrocenes ; Phosphorylated iminophosphoranes ; Dendrimers ; Cations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several R3P=N-P(X)R′2 and Fe[C5H4Ph2P=N-P(X)R′2]2 derivatives (X = S, O) are readily obtained from Staudinger reactions between phosphanes and N3-P(X)R′2. The P=N-P=X groups are easily alkylated on the × atom with methyl or isopropyl triflates. The alkylation induces a lengthening of the P-X bond, as shown by X-ray diffraction studies. This corresponds to a weakening of the P-X bond which can be cleaved with P(NMe2)3 to yield [P=N-P:] linkages. The presence of tricoordinated phosphorus atoms opens the way to a versatile reactivity, including the reaction with alkyl iodides and functionalized azides. These molecules are good models for screening which types of reagents and reactions could be used with macromolecules possessing also P=N-P=X linkages, such as dendrimers.
    Additional Material: 5 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    Synthesis and Homomolecular Metalation of Trialkylsilylphosphanides of Calcium and Barium (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 743-750 
    Details
    ISSN: 1434-1948
    Keywords: Arsenic ; Barium ; Calcium ; Metalations ; NMR spectroscopy ; Phosphorus ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metalation of triisopropylsilylphosphane with bis(tetrahydrofuran-O)calcium bis[bis(trimethylsilyl)amide] in tetrahydropyran (thp) in a molar ratio of 3:2 yields (Me3Si)2NCa[μ-P(H)SiiPr3]3Ca(thp)3 (1) containing a trigonal-bipyramidal Ca2P3 core, the metal atoms occupying apical positions. Reaction of two equivalents of triisopropylsilylphosphane or -arsane with bis(tetrahydrofuran-O)barium bis[bis(trimethylsilyl)amide] in tetrahydrofuran gives the corresponding bis(phosphanide) 2 and bis(arsanide) 3, compounds of the type (thf)3Ba[μ-E(H)SiiPr3]Ba(thf)2E(H)SiiPr3 with E = P, As. The equimolar reaction of (tri-tert-butylsilyl)phosphane with (thf)2Ba[N(SiMe3)2]2 in toluene yields heteroleptic dimeric (thf)2Ba[N(SiMe3)2][P(H)SitBu3] (4). Addition of a further equivalent of H2PSitBu3 leads to the formation of homoleptic (thf)nBa[P(H)SitBu3]2 (5). Dissolution of the latter in aromatic hydrocarbons leads to the elimination of H2PSitBu3, yielding dimeric (thf)Ba3(PSitBu3)2[P(H)SitBu3]2 (6). The inner core of 6 consists of the tetramer (BaPSitBu3)4 based on a Ba4P4 heterocubane unit, two opposite faces being capped with (thf)Ba[P(H)SitBu3]2 molecules.
    Additional Material: 6 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    Synthesis, X-ray Crystal Structures and Reactivity Towards Alkynes of Gold(I)-Phosphinine Complexes (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2233-2241 
    Details
    ISSN: 1434-1948
    Keywords: Phosphorus ; Heterocycles ; Phosphinines ; Gold ; Cycloadditions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The coordination behaviour of 2,6-disilyl-substituted phosphinines towards gold(I) has been examined. The reaction of the bis(trimethylsilyl)phosphinine 1 with [AuCl(SMe2)] gives the corresponding AuCl derivative 2. X-ray crystal structure analysis reveals that the aromaticity of the phosphinine ring is slightly reduced as a result of the poor π-back bonding ability of the AuCl fragment. The same phenomenon is observed in the cationic complex [Au(1)2][GaCl4] (3) which was readily prepared by reaction of two equivalents of 1 with [AuCl(SMe2)] followed by treatment with GaCl3 at low temperature. Reaction of 2,6-bis(phenylethynyldimethylsilyl)phosphinine (4) with the same precursor leads similarly to the complex [AuCl(4)] (5). Interestingly, this complex dimerizes upon crystallization to give the bis(phosphabarrelene) complex 6, also structurally characterized. The formation of 6 results from a [4 + 2] cycloaddition between one alkynyl group of each phosphinine with the other phosphinine subunit. The formation of the cationic complex [Au(4)][GaCl4] (8) occurs under classical conditions but it disproportionates to give the cationic complex [Au(4)2][GaCl4] (9) and colloidal gold deposition. The formation of 9 has been ascertained by treating 8 with one equivalent of ligand 4. Additionally, 9 can also be obtained in a straightforward fashion by treating two equivalents of 4 with [AuCl(SMe2)] followed by treatment with GaCl3 at low temperature. The structure of 9 has been elucidated. Despite a particular arrangement of the alkyne groups which encapsulate the gold coordination sphere, no gold-alkyne interactions are visible.
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  • 17
    Electronic Resource
    Electronic Resource
    The Dramatic Influence of Diamidoamine Ligands on the Structure and Reactivity of Low-Valent Tin and Bismuth Derivatives (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 2295-2299 
    Details
    ISSN: 1434-1948
    Keywords: Lewis acids ; Bismuth ; Aluminum ; Phosphorus ; Tin ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dilithium salts of N-methyl-N′,N′′-bis(diisopropyl)- and -(trimethylsilyl)-diethylenetriamine 1a,b react with SnCl2 affording the corresponding stannylenes 2a,b in 60 and 80% yield, respectively. Compound 1b also reacts with BiCl3 to give the bismuth chloride 5 (90% yield). Derivatives 2b and 5 have a symmetrical bicyclic structure and are monomeric both in solution and in the solid state. When 2b is treated with BiCl3 or PCl3, an oxidation reaction leads to the hypercoordinated tin(IV) dichloride 3 (58% yield), or a transmetallation gives rise to the oniophosphane 4 (95% yield), respectively. Transmetalation reactions also occurred when 5 was treated with AlCl3, GaCl3 or SnCl2 affording the corresponding aluminum chloride 6 (81% yield), gallium chloride 7 (38% yield) or tin dichloride 3 (38% yield). The observed reactivity for 2 and 5 is compared to that reported for Veith's stannylene or bismuth chloride.
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  • 18
    Electronic Resource
    Electronic Resource
    Intramolecular Donor-Assisted Cyclization of Organotin Compounds (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 887-898 
    Details
    ISSN: 1434-1948
    Keywords: Tin ; Phosphorus ; Intramolecular coordination ; O ligands ; Heterocycles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New intramolecularly coordinated organotin compounds containing the monoanionic O,C,O-coordinating ligand {4-tert-Bu-2,6-[P(O)(OEt)2]2C6H2}- have been synthesized by substitution reactions starting from organotin halides. In view of the enhanced reactivity of the intramolecularly coordinated compounds {4-tert-Bu-2,6-[P(O)(OEt)2]2C6H2}SnR2R′ (2, R = Ph, R′ = CH2SiMe3; 3, R = R′ = Ph; 6, R = R′ = Cl), cationic tin species are suggested to occur as intermediates in the formation of the heterocyclic compounds [1(Sn),3(P)-Ph2SnOP(O)(OEt)-5-tert-Bu-7-P(O)(OEt)2]C6H2 (8), [1(Sn), 3(P)-Ph(Me3SiCH2)SnOP(O)(OEt)-5-tert-Bu-7-P(O)(OEt)2]C6H2 (15), and {[1(Sn),3(P)-Cl2SnOP(O)(OEt)-5-tert-Bu-7-P(O)(OEt)]C6H2}2 (16). The latter compounds are formed by intramolecular cyclizations of pentacoordinate cationic tin species under elimination of ethyl halide. Furthermore, the synthesis of [1(Sn),3(P)-Ph2SnOP(O)(OH)-5-tert-Bu-7-P(O)(OH)2]C6H2 (13) is described. Reaction of 8 with an excess of Me3SiBr leads to the unexpected formation of {2-[P(O)(OEt)(OSiMe3)]-4-tert-Bu-6-[P(O)(OEt)2]C6H2}SnPhBr2 (9) as a result of an O-Sn bond cleavage initiated by Me3SiBr and subsequent reaction of the intermediate with further Me3SiBr under Sn-C bond cleavage. The high donor capacity and the rigidity of the new ligand {4-tert-Bu-2,6-[P(O)(OEt)2]2C6H2}- are demonstrated by X-ray diffraction analyses of the tetraorganotin compound 2 and the monoorganotin trichloride 6. Furthermore, the molecular structures of the 2,3,1-oxaphosphastannoles 8 and 16 are discussed.
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  • 19
    Electronic Resource
    Electronic Resource
    Synthesis and Characterisation of tetrahedro-Tetraphosphorus Complexes of Rhenium - Evidence for the First Bridging Complex of White Phosphorus (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 931-933 
    Details
    ISSN: 1434-1948
    Keywords: Phosphorus ; Rhenium ; 31P-NMR spectroscopy ; Tripodal polyphosphanes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of white phosphorus with [(triphos)Re(CO)2(OTf)] (1) in dichloromethane affords the new tetraphosphorus complex [(triphos)Re(CO)2(η1-P4)](OTf) (2) [triphos = MeC(CH2PPh2)3; OTf = OSO2CF3]. Compound 2 reacts with a second equivalent of 1 to give the binuclear complex [{(triphos)Re(CO)2}2(μ,η1,η1-P4)](OTf)2 (3) in which a tetrahedro-P4 ligand behaves as tethering unit between two [(triphos)Re(CO)2]+ moieties. Complexes 2 and 3 represent the first soluble metal complexes of the tetraphosphorus molecule where the P4 ligand has not undergone any major modification.
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  • 20
    Electronic Resource
    Electronic Resource
    Cobalt Complexes with 1,3-Bis(trimethylsilyl)cyclopentadienyl and Substituent-Free Pn Ligands (1999)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1999 (1999), S. 945-949 
    Details
    ISSN: 1434-1948
    Keywords: Phosphorus ; Pn ; C5H3(SiMe3)2 ligands ; Cobalt ; Coordination chemistry ; Crystallography ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal or photochemical reaction of [Cp′′Co(CO)2] (1) [Cp′′ = C5H3(SiMe3)2-1,3] with white phosphorus (P4) gives [{Cp′′Co}2(P5-P5){CoCp′′}2] (2) and [{Cp′′Co}3P4(μ-CO)] (3) as well as [{Cp′′Co}2(μ-η2:η2-P2)2] (4). Cobalt complexes 2, 3, and 4 have been characterized by an X-ray crystal-structure determination.
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  • 21
    Electronic Resource
    Electronic Resource
    Studies of iron transport by arbuscular mycorrhizal hyphae from soil to peanut and sorghum plants (1998)
    Springer
    Mycorrhiza 8 (1998), S. 35-39 
    Details
    ISSN: 1432-1890
    Keywords: Key words Arbuscular mycorrhiza ; Iron ; Peanut ; Phosphorus ; Sorghum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The influence of an arbuscular mycorrhizal (AM) fungus on phosphorus (P) and iron (Fe) uptake of peanut (Arachis hypogea L.) and sorghum (Sorghum bicolor L.) plants was studied in a pot experiment under controlled environmental conditions. The plants were grown for 10 weeks in pots containing sterilised calcareous soil with two levels of Fe supply. The soil was inoculated with rhizosphere microorganisms only or with rhizosphere microorganisms together with an AM fungus (Glomus mosseae [Nicol. & Gerd.] Gerdemann & Trappe). An additional small soil compartment accessible to hyphae but not roots was added to each pot after 6 weeks of plant growth. Radiolabelled P and Fe were supplied to the hyphae compartment 2 weeks after addition of this compartment. After a further 2 weeks, plants were harvested and shoots were analysed for radiolabelled elements. In both plant species, P uptake from the labelled soil increased significantly more in shoots of mycorrhizal plants than non-mycorrhizal plants, thus confirming the well-known activity of the fungus in P uptake. Mycorrhizal inoculation had no significant influence on the concentration of labelled Fe in shoots of peanut plants. In contrast, 59Fe increased in shoots of mycorrhizal sorghum plants. The uptake of Fe from labelled soil by sorghum was particularly high under conditions producing a low Fe nutritional status of the plants. These results are preliminary evidence that hyphae of an arbuscular mycorrhizal fungus can mobilise and/or take up Fe from soil and translocate it to the plant.
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    URL: http://dx.doi.org/10.1007/s005720050208
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  • 22
    Electronic Resource
    Electronic Resource
    Effect of root exudate fractions from P-deficient and P-sufficient onion plants on root colonisation by the arbuscular mycorrhizal fungus Gigaspora margarita (1998)
    Springer
    Mycorrhiza 8 (1998), S. 67-70 
    Details
    ISSN: 1432-1890
    Keywords: Key words Allium cepa ; Appressorium ; Arbuscular mycorrhiza ; Root colonisation ; Phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The effect of root exudates from P-deficient onion on root colonisation by an arbuscular mycorrhizal fungus was examined. Onions (Allium cepa L.) were grown in solution culture at phosphorus concentrations of 0 (P0) and 2 (P2) mg P l–1. Root exudates were collected and fractionated with Amberlite XAD-4 resin to give EtOH and water soluble fractions. Onions inoculated with the arbuscular mycorrhizal fungus Gigaspora margarita Becker & Hall were grown with or without (control) root exudates and exudate fractions in a growth chamber. After 24 days, arbuscular mycorrhiza levels and appressoria formation had increased in plants treated with P0-root exudate or the P0-EtOH fraction when compared to corresponding P2 treatments or control plants. P0 and P2 water-soluble fractions did not significantly affect either aspect of fungal development. These results suggest that hydrophobic compounds found in root exudates from P-deficient onion increase appressorium formation and, therefore, enhance mycorrhiza development.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s005720050214
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  • 23
    Electronic Resource
    Electronic Resource
    Patterns of arbuscular mycorrhiza colonisation of the roots of Hyacinthoides non-scripta after disruption of soil mycelium (1998)
    Springer
    Mycorrhiza 8 (1998), S. 87-91 
    Details
    ISSN: 1432-1890
    Keywords: Key words Acaulospora ; Hyacinthoides non-scripta ; Bluebell ; Disturbance ; Glomus ; Fine endophytes ; Phosphorus ; Scutellospora
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  Early-season colonisation of new roots of Hyacinthoides non-scripta (L.) Chouard ex Rothm. was investigated to determine how arbuscular mycorrhizal symbiosis is re-established after the annual root system is shed. During the rootless phase in summer, colonies of bulbs were removed and replanted after the soil around and below the bulb had been mixed (major disturbance) so as to disrupt the external mycelium of arbuscular mycorrhizal (AM) fungi. As a minor disturbance treatment, top soil was removed, bulbs were turned or not in their growth position with as little other disturbance as possible, and the top soil replaced. Control plants were left undisturbed. Half of the plants were harvested 3–4 weeks after the onset of root emergence. Populations of all AM fungi in roots were greatly reduced by major disturbance, whilst those in other treatments and controls were unaffected. At the second harvest, in spring, when shoots had emerged, root colonisation by fine endophytes and Scutellospora morphotypes developed in all treatments, whereas that of Acaulospora morphotypes remained low after major disturbance. Disturbance treatments delayed the appearance, at the second harvest, of mycorrhizas with degenerate arbuscules. Leaf phosphorus concentration was unaffected by soil disturbance, possibly due to partial recovery of AM fungal populations or buffering by resources stored in the bulb.
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    URL: http://dx.doi.org/10.1007/s005720050217
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  • 24
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    Seasonal mycorrhizal colonization of winter wheat and its effect on wheat growth under dryland field conditions (1998)
    Springer
    Mycorrhiza 8 (1998), S. 139-144 
    Details
    ISSN: 1432-1890
    Keywords: Key words Winter wheat ; Mycorrhiza ; Phosphorus ; Dryland
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  A field experiment was conducted to determine the seasonal patterns of arbuscular mycorrhiza (AM) in a dryland winter wheat (Triticum aestivum L.) system and to determine wheat growth and P uptake responses to inoculation with mycorrhizal fungus. Broadcast-incorporated treatments included (1) no inoculation with mycorrhizal fungus, with and without P fertilizer, and (2) mycorrhizal fungal inoculation at a rate of 5000 spores of Glomus intraradices (Schenck and Smith), per 30 cm in each row, with and without fertilizer P. Winter wheat was seeded within a day after treatments were imposed, and roots were sampled at five growth stages to quantify AM. Shoot samples were also taken for determination of dry matter, grain yield and yield components, and N and P uptake. No AM infection was evident during the fall months following seeding, which was characterized by low soil temperature, while during the spring, the AM increased gradually. Increases in wheat grain yields by enhanced AM were of similar magnitude to the response obtained from P fertilization. However, responses differed at intermediate growth stages. At the tillering stage, P uptake was mainly increased by P fertilization but not by fungal inoculation. At harvest, enhanced AM increased P uptake regardless of whether or not fertilizer P was added. The AM symbiosis increased with rising soil temperatures in the spring, in time to enhance late-season P accumulation and grain production.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s005720050226
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  • 25
    Electronic Resource
    Electronic Resource
    Effect of phosphate and the arbuscular mycorrhizal fungus Glomus intraradices on disease severity of root rot of peas (Pisum sativum) caused by Aphanomyces euteiches (1998)
    Springer
    Mycorrhiza 8 (1998), S. 169-174 
    Details
    ISSN: 1432-1890
    Keywords: Key words Peas ; Aphanomyces euteiches ; Phosphorus ; PAGE ; Isozymes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The effects of inorganic phosphate levels and the presence of arbuscular mycorrhiza on disease severity of Aphanomyces euteiches in pea roots were studied. Disease severity on roots and epicotyl as well as the oospore number within infected root tissue were correlated with the phosphorus (P) level in the growth medium. The arbuscular mycorrhizal fungus Glomus intraradices increased P uptake and the P concentration in the plant but reduced disease development in peas. Polyacrylamide gel electrophoresis followed by densitometry of glucose-6-phosphate dehydrogenase specific to A.euteiches was used to measure the activity of the pathogen in roots. The enzyme activity increased with disease severity and disease incidence, except in plants supplemented with P at the highest level, where a peak in activity was seen 12 days after inoculation with the pathogen, followed by a decrease in activity. The epicotyl of mycorrhizal plants showed a reduction in disease severity although this part of the plants was not mycorrhizal. Thus, an induced systemic factor may be responsible for increased resistance in mycorrhizal plants.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s005720050230
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  • 26
    Electronic Resource
    Electronic Resource
    Edaphic factors as determinants for the distribution of intrinsic antibiotic resistance in a cowpea rhizobia population (1998)
    Springer
    Biology and fertility of soils 27 (1998), S. 386-392 
    Details
    ISSN: 1432-0789
    Keywords: Key words Rhizobia ; Cowpea ; Antibiotic resistance ; Phosphorus ; Aluminium
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract  A large collection of cowpea rhizobia strains was obtained from soil samples collected from either a semi-arid or a tropical rain forest area located at about the same latitude in the north-eastern region of Brazil and evaluated for their intrinsic antibiotic resistance to eight commercial antibiotics. The aim of this study was to correlate antibiotic resistance of native rhizobia strains to edaphic-climatic factors as a way to establish suitable inoculants for specific areas. A large diversity regarding intrinsic antibiotic resistance was found, and 17 clusters were identified as varying from sensitive to gradually resistant up to 500 μg·ml–1 of the antibiotics tested. Clustering analysis did not show any pattern related to the geographic region where isolates have been obtained. On the other hand, an increase in the antibiotic-resistant rhizobia population was associated with an increase in soil P and Al contents. lsolates which were sensitive to spectinomycin, ampicillin, streptomycin, chloramphenicol and tetracycline were present at higher rates in soils devoid of Al. Rhizobia bacteria producing mucus type I (fluid and capable of spreading over the solid media) were found preferentially in soil with Al concentrations up to 36 mg·kg–1, diminishing quickly at higher levels.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s003740050448
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  • 27
    Electronic Resource
    Electronic Resource
    Soil-plant interactions in a neotropical mangrove forest: iron, phosphorus and sulfur dynamics (1998)
    Springer
    Oecologia 115 (1998), S. 553-563 
    Details
    ISSN: 1432-1939
    Keywords: Key words Mangrove species zonation ; Sulfate reduction ; Pyrite formation ; Phosphorus ; Decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract We examined soil porewater concentrations of sulfate, alkalinity, phosphorus, nitrogen, and dissolved organic carbon and solid phase concentrations of pyrite in relation to mangrove species distributions along a 3.1-km-long transect that traversed a 47.1-km2 mangrove forest in the Dominican Republic. Iron, phosphorus, and sulfur dynamics are closely coupled to the activity of sulfate-reducing bacteria, the primary decomposers in anoxic soils of mangrove ecosystems. Patterns in the chemistry data suggested that sulfate reduction rates and storage of reduced sulfur were greater in the inland basin forest dominated by Laguncularia racemosa than the Rhizophora mangle dominated forest of the lower tidal region. The distribution of Laguncularia was significantly correlated with concentrations of total phosphorus (r= 0.99) and dissolved organic carbon (r= 0.86), alkalinity (r= 0.60), and the extent of sulfate depletion (r= 0.77) in the soil porewater and soil pyrite concentrations (r= 0.72) across the tidal gradient. Leaf tissue chemistry of Laguncularia was characterized by lower C:N and C:P ratios that could fuel the higher rates of decomposition in the Laguncularia-dominated forest. We suggest that a plant-soil-microbial feedback contributes to the spatial patterning of vegetation and soil variables across the intertidal zone of many mangrove forest communities.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004420050553
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  • 28
    Electronic Resource
    Electronic Resource
    Nutrient relations in calcareous grassland under elevated CO2 (1998)
    Springer
    Oecologia 116 (1998), S. 67-75 
    Details
    ISSN: 1432-1939
    Keywords: Key words Dinitrogen fixation ; Plant functional types ; legumes ; Nutrient limitation ; Phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Plant nutrient responses to 4 years of CO2 enrichment were investigated in situ in calcareous grassland. Beginning in year 2, plant aboveground C:N ratios were increased by 9% to 22% at elevated CO2 (P 〈 0.01), depending on year. Total amounts of N removed in biomass harvests during the first 4 years were not affected by elevated CO2 (19.9 ± 1.3 and 21.1 ± 1.3 g N m−2 at ambient and elevated CO2), indicating that the observed plant biomass increases were solely attained by dilution of nutrients. Total aboveground P and tissue N:P ratios also were not altered by CO2 enrichment (12.5 ± 2 g N g−1 P in both treatments). In contrast to non-legumes (〉98% of community aboveground biomass), legume C/N was not reduced at elevated CO2 and legume N:P was slightly increased. We attribute the less reduced N concentration in legumes at elevated CO2 to the fact that virtually all legume N originated from symbiotic N2 fixation (%Ndfa ≈ 90%), and thus legume growth was not limited by soil N. While total plant N was not affected by elevated CO2, microbial N pools increased by +18% under CO2 enrichment (P = 0.04) and plant available soil N decreased. Hence, there was a net increase in the overall biotic N pool, largely due increases in the microbial N pool. In order to assess the effects of legumes for ecosystem CO2 responses and to estimate the degree to which plant growth was P-limited, two greenhouse experiments were conducted, using firstly undisturbed grassland monoliths from the field site, and secondly designed `microcosm' communities on natural soil. Half the microcosms were planted with legumes and half were planted without. Both monoliths and microcosms were exposed to elevated CO2 and P fertilization in a factored design. After two seasons, plant N pools in both unfertilized monoliths and microcosm communities were unaffected by CO2 enrichment, similar to what was found in the field. However, when P was added total plant N pools increased at elevated CO2. This community-level effect originated almost solely from legume stimulation. The results suggest a complex interaction between atmospheric CO2 concentrations, N and P supply. Overall ecosystem productivity is N-limited, whereas CO2 effects on legume growth and their N2 fixation are limited by P.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004420050564
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  • 29
    Electronic Resource
    Electronic Resource
    Lattice Monte Carlo simulations as link between ab-initio calculations and macroscopic behavior of dopants and defects in silicon (1998)
    Springer
    Journal of computer-aided materials design 5 (1998), S. 81-88 
    Details
    ISSN: 1573-4900
    Keywords: Aggregation ; Arsenic ; Diffusion ; Lattice Monte Carlo ; Phosphorus ; Silicon ; Vacancy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In this work, we show that lattice Monte Carlo simulations can be used to span the time and distance scales between underlying atomistic processes and macroscopic diffusion behavior. We use ab- initio calculations of binding energies versus configuration to calculate hopping rates of vacancies for use in lattice Monte Carlo (LMC) simulations of diffusion and aggregation in silicon. The LMC simulations consider the biased nature of vacancy hop frequencies in the neighborhood of dopants, with interactions up to sixth-nearest- neighbor distances included. We use these simulations to investigate the expected macroscopic diffusion behavior, as well as the process by which dopant/defect aggregation occurs. Specific phenomena investigated include collective behavior leading to greatly enhanced diffusivity at high doping levels, the time dependence of effective diffusivity due to the formation of dopant/vacancy clusters, and dopant fluxes in the presence of a vacancy gradient.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1008689130758
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  • 30
    Electronic Resource
    Electronic Resource
    Mapping of QTLs for phosphorus-deficiency tolerance in rice (Oryza sativa L.) (1998)
    Springer
    Theoretical and applied genetics 97 (1998), S. 777-783 
    Details
    ISSN: 1432-2242
    Keywords: Key words Rice ; QTL ; Phosphorus ; Use efficiency ; Deficiency tolerance
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  Phosphorus (P) deficiency of soils is a major yield-limiting factor in rice production. Increasing the P-deficiency tolerance of rice cultivars may represent a more cost-effective solution than relying on fertilizer application. The objective of this study was to identify putative QTLs for P-deficiency tolerance in rice, using 98 backcross inbred lines derived from a japonica×indica cross and genotyped at 245 RFLP marker loci. Lines were grown on P-deficient soil and P uptake, internal P-use efficiency, dry weight, and tiller number were determined. Three QTLs were identified for dry weight and four QTLs for P uptake, together explaining 45.4% and 54.5% of the variation for the respective traits. Peaks for both traits were in good agreement which was to be expected considering the tight correlation of r=0.96 between dry weight and P uptake. For both traits the QTL linked to marker C443 on chromosome 12 had a major effect. Two of the three QTLs detected for internal P-use efficiency, including the major one on chromosome 12, coincided with QTLs for P uptake; however, whereas indica alleles increased P uptake they reduced P-use efficiency. We concluded that this was not due to the tight linkage of two genes in repulsion but rather due to an indirect effect of P uptake on P-use efficiency. Most lines with high use efficiency were characterized by very low P uptake and dry weight and apparently experienced extreme P-deficiency stress. Their higher P-use efficiency was thus the result of highly sub-optimal tissue-P concentrations and did not represent a positive adaptation to low P availability. The number of tillers produced under P deficiency is viewed as an indirect indicator of P-deficiency tolerance in rice. In addition to the major QTL on chromosome 12 already identified for all other traits, two QTLs on chromosome 4 and 12 were identified for tiller number. Their position, however, coincided with QTLs for tiller number reported elsewhere under P-sufficient conditions and therefore appear to be not related to P-deficiency tolerance. In this study P-deficiency tolerance was mainly caused by differences in P uptake and not in P-use efficiency. Using a trait indirectly related to P-deficiency tolerance such as tiller number, we detected a major QTL but none of the minor QTLs detected for P uptake or dry weight.
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    URL: http://dx.doi.org/10.1007/s001220050955
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  • 31
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    Sutural mineralization of rat calvaria characterized by atomic-force microscopy and transmission electron microscopy (1998)
    Springer
    Cell & tissue research 294 (1998), S. 93-97 
    Details
    ISSN: 1432-0878
    Keywords: Key words Calvaria ; Mineralization ; Calcium ; Phosphorus ; Apatite ; Atomic-force microscopy ; Transmission electron microscopy ; Rat (Sprague Dawley)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Abstract  The application of transmission electron microscopy (TEM) and atomic-force microscopy (AFM) aid the acquisition of detailed structural information on the process of hard tissue formation. The sutural mineralization of rat calvaria is taken as a model for a collagen-related mineralization system. After cryofixation or chemical fixation an anhydrous tissue preparation technique with no staining procedures is used. The atomic-force microscope and the transmission electron microscope are used for structural analysis of the mineralizing region of the sutural tissue. With the application of AFM the collagen macroperiod is shown to be well represented in the unmineralized sutural tissue. At the mineralization front the collagen fibrils are found to be thickened and to change to a characteristic stacked platelet structure. Using TEM the macroperiod is faintly visible before mineral crystallites have formed and is more prominent after the apatite crystallization has started in the fibrils. In this step a needle-like structure of the newly formed apatitic crystals is visible.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004410051159
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  • 32
    Electronic Resource
    Electronic Resource
    Comparison of nutrient losses into the water from rainbow trout culture based on fresh Baltic herring, moist and dry diets (1998)
    Springer
    Aquaculture international 6 (1998), S. 441-450 
    Details
    ISSN: 1573-143X
    Keywords: Cage culture ; Dietary lipid ; Dietary water ; Feeding frequency ; Moist diets ; Nitrogen ; Phosphorus ; Rainbow trout (Oncorhynchus mykiss)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract The nutrient losses into the water from rainbow trout (Oncorhynchus mykiss) cage culture using locally caught low-fat Baltic herring, herring-based moist diets and fishmeal-based dry diets were estimated. Feeding with herring led to nitrogen and phosphorus losses into the water twice as high as those feeding with dry pellets (78–162 versus 37–39 g N and 15–39 versus 7–18 g P per kg growth). This was supported by direct measurements of ammonia and phosphate excretion. Increasing feeding frequencies resulted in increased nutrient losses irrespective of diet. Increasing dietary lipid level had a more pronounced effect in reducing the expected nutrient losses in dry pellets than herring. The reduction within the herring was approximately 18% on average for nitrogen and 25% for phosphorus losses. Dietary water content did not affect the nutrient losses. © Rapid Science Ltd. 1998
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1009283401505
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    Electronic Resource
    Fluxionality and Phosphane Arm-off Reactions of Octahedral Ruthenium(II) Complexes with the Tripodal Polyphosphane MeC(CH2PPh2)3 (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 407-414 
    Details
    ISSN: 1434-1948
    Keywords: Ruthenium ; Phosphorus ; Triphos complexes ; Fluxionality ; Arm-off dissociation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Structural fluxionality is apparent in the 1H- and 31P-NMR spectra of compounds of the type [Ru(L)(MeCN)(triphos)](CF3SO3), 2-5, at 25°C, where L represents a diorganyldithiocarbamate or a heterocyclic κ2N,S coordinating thioamide. In contrast, complexes [Ru(Et2NCS2)(Y)(triphos)]n+ (6, n = 1, Y = CO; 7, n = 0, Y = CN-; 8, n = 0, Y = H-) are stereochemically rigid in solution at this temperature, indicating that MeCN dissociation must occur for the crowded octahedral coordination spheres of 2-5. Reaction of [Ru(MeCN)3(triphos)](CF3SO3)2, 1, with Na(Et2NCS2) at a 1:2 molar ratio yields [Ru(Et2NCS2-κ2S)(Et2NCS2-κS)(triphos)], 9, which slowly converts to [Ru(Et2NCS2-κ2S)2(triphosO-κ2P)], 10, on recrystallization from ethanol/acetone under air [triphosO is O=P(Ph)2CH2C(CH3)(CH2PPh2)2]. A similar κ3P→κ2P arm-off dissociation leads to the formation of [Ru(mpy-κ2N,S)2(triphosO-κ2P)] (13) and [Ru(mmim-κ2N,S)2(triphosO-κ2P)] (14) (Hmpy = 2-mercaptopyridine, Hmmim = 2-mercapto-1-methylimidazole). Crystal structures are reported for [Ru(mbt-κ2N,S)(MeCN)(triphos-κ3P)](CF3SO3) (4) (Hmbt = 2-mercaptobenzothiazole), [Ru(mpym-κ2N,S)(mpym-κS)(triphos-κ3P)] (11) (Hmpym = 2-mercaptopyrimidine) and 14, the latter of which is present as the OC-6-13 isomer.
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  • 34
    Electronic Resource
    Electronic Resource
    The Triphosphide (tBu3Si)2P3Na: Formation, X-ray and Ab initio Structure Analyses, Protonation and Oxidation to Triphosphane (tBu3Si)2P3H and Hexaphosphanes (tBu3Si)4P6⋆ (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 833-841 
    Details
    ISSN: 1434-1948
    Keywords: Silicon ; Phosphorus ; Oligophosphides and -phosphanes ; NMR spectra ; X-ray structure analysis ; Ab initio calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The violet THF adduct (tBu3Si)2P3Na(THF)4 (1a) of the triphosphide (tBu3Si)2P3Na (1) is prepared, (i) by protolysis of the tetraphosphide (tBu3Si)2P4Na2 (2) with an equimolar amount of CF3CO2H in THF (transformation of 2 into 1), (ii) by the reaction of tBu3SiNa and the oligophosphane (tBu3SiP3)n in THF (building-down of Pn), and (iii) by the action of tBu3SiNa on PCl3 in THF (building-up of Pn). According to X-ray structural analysis, the SiPPPSi skeleton of the anionic part [tBu3SiPPPSitBu3]- of 1a is W-shaped with two P-P 11/2 bonds; in addition, 1a contains a planar deltoid P3Na backbone with the 4 THF molecules coordinated to Na. The protolysis of 1a leads to cyclotriphosphane (tBu3Si)2P3H (11), and the oxidation of 1a leads to 1,1′-bicyclotriphosphane (tBu3Si)2P3-P3(SitBu3)2 (12) as the main product and bicyclo[3.1.0]hexaphosphane (tBu3Si)4P6 (13) as an isomer of 12. The structures of 11, 12, and 13 as well as the structure of 1a have been unambiguously determined by 31P-NMR studies. Ab initio structure and energy calculations show that the acyclic P3H2- with allylic conjugation and P-P 11/2 bonds is thermodynamically more stable than the cyclic isomer whereas, in contrast, the neutral compound P3H3 prefers the cyclic form. The exceptional downfield shift of the NMR signal of the central phosphorus in 1a is in agreement with DFT NMR calculations for a model compound [H3SiPPPSiH3]Na with P-P 11/2 bonds.
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    Electronic Resource
    A Convenient Synthesis of Phosphonic Anhydrides - Trimers [RPO2]3 (R = tert-Butyl, 2-Methylphenyl, 2,4,6-Trimethylphenyl): Their Structures and Reaction Products (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 361-366 
    Details
    ISSN: 1434-1948
    Keywords: Phosphorus ; Phosphonic anhydrides ; Oligophosphonic acids ; Peptide synthesis ; Solid-state structures ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By reaction of RP(O)Cl2 with RP(O)(OSiMe3)2, phosphonic anhydrides (RPO2)3 (R = tBu, 2-methylphenyl, 2,4,6-trimethylphenyl) 1a-c are conveniently obtained. In contrast to 1b and 1c, compound 1a is remarkably stable against protolysis. Intermediates of hydrolysis of 1a, namely tris(tert-butyl)triphosphonic acid (2) and bis(tert-butyl)diphosphonic acid (3), can also be isolated in good yield. The structures of 1-3 were determined mainly by NMR spectroscopy (1 H, 13C, 31P). Assuming an energetic preference for the chair conformations in solution, and considering the steric requirements of the bulky substituents R, configurations Ia (point group Cs, two R in equatorial positions) for 1a and b, and IIa (point group C3v, all R equatorial) for 1c are suggested. - Reaction of 1a with N-benzyloxycarbonylglycine (4) in methanol affords strong evidence that in the first step of peptide synthesis with (RPO2)3, a mixed anhydride of triphosphonic acid and the N-protected amino acid is formed. - The crystal structure of 1a (monoclinic, space group P21/n) widely corresponds to the suggested configuration Ia, but reveals an envelope conformation for the six-membered ring with a P3O2 plane in the crystal. In the crystal structure of the octahydrate of the disodium salt of 2 (monoclinic, space group P21/c), it can be seen that the polar end groups of the anions [tBu3P3O7]2- together with the water molecules and the Na+ cations, form hydrogen-bonded double-layers, strictly separated from each other by the non-polar tert-butyl groups of the anions.
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    Electronic Resource
    Electronic Resource
    Oligomeric Solvent-Free Magnesium Bis(phosphanides) - Molecular Structure of Trimeric Magnesium Bis[bis(trimethylsilyl)phosphanide] (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 517-521 
    Details
    ISSN: 1434-1948
    Keywords: Bis(silyl)phosphanes ; Magnesium ; NMR spectroscopy ; Oligomers ; Phosphorus ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The metathesis reaction of (dme)LiPH2 and chlorodiisopropylsilane yields HP(SiHiPr2)2 (1) and P(SiHiPr2)3 (2). The metalation of 1 by n/sec-dibutylmagnesium in heptane leads to the formation of dimeric magnesium bis[bis(diisopropylsilyl)phosphanide] [(3)2]. A toluene solution of magnesium bis[bis(trimethylsilyl)phosphanide] (4) shows a dimer-trimer equilibrium in the 31P{1H}-NMR spectrum at -40°C with an increasing amount of the dimer with increasing temperature. A molecular mass determination by freezing-point depression in benzene yields a value of 516 g·mol-1, which lies between a monomeric and a dimeric molecule. Cooling of the toluene solution to -30°C leads to the precipitation of single crystals of monoclinic {(Me3Si)2P-Mg[μ-P(SiMe3)2]2}2Mg [(4)3].
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  • 37
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    Electronic Resource
    Phosphorus-Bridged Dinuclear Tungsten Amino(aryl)carbene Complexes - New Precursors for (2H-Azaphosphirene)tungsten Complexes bearing a σ-P-Bonded Cp* Group⋆ (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 2005-2012 
    Details
    ISSN: 1434-1948
    Keywords: Carbene complexes ; Tungsten ; Phosphorus ; 2H-Azaphosphirene complexes ; Cyclization ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The first syntheses of pentacarbonyl[2-(pentamethyl-2,4-cyclopentadien-1-yl)-2H-azaphosphirene]tungsten complexes are reported, using a one-pot reaction of dichloro(pentamethyl-2,4-cyclopentadien-1-yl)phosphane (Cp*PCl2) with triethylamine and {[amino(aryl)carbene]pentcarbonyltungsten(0)}. [Pentamethyl-2,4-cyclopentadien-1-yl]phosphanediyl-bridged dinuclear carbene complexes are formed as long-lived intermediates, which, by elimination and rearrangement reactions, led to the final products. If traces of water were present, then by-products were formed; in one case, a dinuclear carbene complex with a P(Cp*)-O-P(Cp*) bridging unit was isolated. Under ordinary reaction conditions 2H-azaphosphirene complexes are slowly transformed into {pentacarbonyl[chloro(pentamethyl-2,4-cyclopentadien-1-yl)phosphane]tungsten(0)}. NMR-spectroscopic and single-crystal X-ray structural data of some dinuclear carbene complexes and 2-(pentamethyl-2,4-cyclopentadien-1-yl)-2H-azaphosphirene complexes are presented.
    Additional Material: 6 Ill.
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    Electronic Resource
    1,2-Diphosphetes with Unusual Structures - A Quantum Chemical Investigation of Bonding Properties⋆ (1998)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 1998 (1998), S. 951-955 
    Details
    ISSN: 1434-1948
    Keywords: Ab initio calculations ; Phosphorus ; Strained molecules ; Substituent effects ; Pericyclic reactions ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: According to quantum chemical calculations at an ab initio level parent 1,2-diphosphete is slightly more stable than its corresponding 1,4-diphosphabutadiene structural isomer. The quantum chemical calculations indicate that substituents at phosphorus and to a much less extent at carbon exert strong influences on the equilibrium geometries of 1,2-diphosphete structures: π donors at phosphorus strongly elongate the P-P bond while electronegative substituents at phosphorus increase the interflap angle of the four-membered ring systems, bringing an envelope conformation to the fore. The lengthening of the P-P bond gives rise to a Möbius-type delocalization within the ring moiety.
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  • 39
    Electronic Resource
    Electronic Resource
    Growth response of lentil and wheat to Glomus clarum NT4 over a range of P levels in a Saskatchewan soil containing indigenous AM fungi (1997)
    Springer
    Mycorrhiza 7 (1997), S. 3-8 
    Details
    ISSN: 1432-1890
    Keywords: Key words Glomus clarum NT4 ; Lentil ; Wheat ; Indigenous AMF ; Phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The growth responses of lentil (Lens esculenta L. cv. Laird) and two wheat cultivars (Triticum aestivum L. cv. Laura and Neepawa) to Glomus clarum NT4 in soil containing indigenous arbuscular mycorrhizal fungi (AMF) and fertilized with phosphorus at different (0, 5, 10, 20 ppm) levels was studied in a growth chamber. Soil was inoculated with a monospecific culture of G. clarum NT4 to provide an inoculant:indigenous AMF ratio of ca. 1 : 100. The shoot and root growth, and AMF colonization levels of NT4-inoculated lentil were significantly (P≤0.05) greater than the appropriate control plants in the unfertilized soil at 48 days after planting (DAP). At 95 DAP, NT4 inoculation had significantly increased the shoot dry weight (P≤0.08) and AMF colonization (P≤0.05) of lentil plants receiving 5 mg P kg–1 soil, whereas 20 mg P kg–1 soil reduced the shoot growth of NT4-inoculated plants. The NT4 inoculant had no effect (P≤0.05) on shoot P content, but increased (P≤0.08) the P-use efficiency of lentil plants receiving 5 mg P kg–1 soil. In contrast to the inoculant's effect on lentil, NT4 generally had no positive effect on any of the parameters assessed for wheat cv. Laura at any P level at 48 or 95 DAP. Similarly, there was no positive effect of NT4 on shoot or root growth, or AMF colonization of wheat cv. Neepawa plants at any P level at 48 DAP. However, NT4 inoculation increased the grain yield of Neepawa by 20% (P≤0.05) when fertilized with 20 mg P kg–1 soil. This yield increase was associated with a significant (P≤0.05) reduction in root biomass and a significant (P≤0.05) increase in the grain P content of inoculated plants. Thus, NT4 appears to have a preference for the Neepawa cultivar. Our results show that lentil was more dependent on mycorrhizae than wheat and responded to an AMF inoculant even in soil containing high levels of indigenous AMF. It might, therefore, be possible to develop mixed inoculants containing rhizobia and AMF for field production of legumes.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s005720050156
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  • 40
    Electronic Resource
    Electronic Resource
    Effects of arbuscular mycorrhizal fungi and drought stress on growth and nutrient uptake of two wheat genotypes differing in drought resistance (1997)
    Springer
    Mycorrhiza 7 (1997), S. 83-88 
    Details
    ISSN: 1432-1890
    Keywords: Key words AM ; Drought resistance ; Genotype ; Phosphorus ; Triticum durum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract  The effects of an arbuscular mycorrhizal (AM) fungus and drought stress on the growth, phosphorus, and micronutrient uptake of two wheat genotypes exhibiting differences in drought resistance were investigated. Plants were grown on a low P (4 mg kg–1 soil) silty clay (Typic Xerochrept) soil-sand mix. Mycorrhizal infection was higher under well-watered than under dry soil conditions and the drought-resistant genotype CR057 had a higher mycorrhizal colonization than the drought-sensitive genotype CR006. Total and root dry matter yields and total root length were higher in mycorrhizal than in nonmycorrhizal plants of both genotypes. CR057 had higher total dry matter but not root dry matter than CR006 plants. The enhancement in total dry matter due to AM inoculation was 42 and 39% under well-watered and 35 and 45% under water-stressed for CR057 and and CR006, respectively. For both genotypes, the contents of P, Zn, Cu, Mn, and Fe were higher in mycorrhizal than in nonmycorrhizal plants and higher under well-watered than under dry soil conditions. The enhancement of P, Zn, Cu, Mn, and Fe uptake due to AM inoculation was more pronounced in CR006 than in CR057, particularly under water-stressed conditions. Thus CR006 benefitted from AM infection more than the CR057 under dry soil conditions, despite the fact that CR057 roots were highly infected. It appears that CR006 is more dependent on AM symbiosis than CR057.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s005720050166
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  • 41
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    Electronic Resource
    Isotope techniques to study phosphorus cycling in agricultural and forest soils: a review (1997)
    Springer
    Biology and fertility of soils 24 (1997), S. 1-12 
    Details
    ISSN: 1432-0789
    Keywords: Phosphorus ; Isotope techniques ; Forest P immobilization ; Soil-plant system ; Root activity Nutrient cycling ; Organic P sources
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract A sound understanding of nutrient dynamics in ecosystems is required in order to manage these systems on a sustainable basis. A valuable approach to studying phosphorus (P) dynamics in soil-plant systems has been the use of P isotope techniques. Isotope techniques used for studying P cycling in agricultural and forest soils are reviewed in this paper with particular reference to advances made in the part 15 years. A brief discussion of the properties of P isotopes and their measurements is included together with techniques for measuring exchangeable P in the soil, dissolution and decomposition rates of inorganic and organic P sources applied to the soil, rates of organic P immobilization and mineralization, rates of P release and retention in the soil, root activity and lifter decomposition rates in forest soils, and gene probing and hybridization. Basic principles, assumptions, procedures, limitations and merits of methods are discussed. These techniques have served as or have the potential to be valuable tools for advancing our understanding of P dynamics in soil-plant systems, and for studying the molecular characteristics of microbial communities in relation to the cycling of nutrients in the soil.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01420213
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    Electronic Resource
    Electronic Resource
    Enzymatic release of phosphate from model substrates and P compounds in soil solution from a peaty podzol (1997)
    Springer
    Biology and fertility of soils 24 (1997), S. 183-187 
    Details
    ISSN: 1432-0789
    Keywords: Key words Enzyme ; Hydrolysis ; Ion association ; complex ; Phosphorus ; Soil solution ; Podzol
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Phosphate in solutions of model esters and polyphosphates (glucose phosphate, inositol hexaphosphate, pyrophosphate, ribonucleic acid, tripolyphosphate and trimetaphosphate) was quantitatively released in 〈6 h by acid phosphatase or phytase at pH 5.0. Interference from insoluble, ion association complexes formed between protein in the enzymes and the phosphomolybdenum blue during the colorimetric determination of the molybdate reactive phosphorus released was removed by adding dimethyl sulphoxide. Filtered (0.45 μm) soil solution from a peaty soil contained 590 μg dm–3 total dissolved phosphorus (TDP), of which 13% was molybdate reactive phosphorus (MRP), 26% dissolved organic phosphorus (DOP) and 61% dissolved condensed phosphorus (DCP). When acid phosphatase was added to the soil solution under the conditions used to hydrolyse the model compounds, MRP increased to 54% of the TDP in about 10 h and then remained constant. From a mass balance, at least 25% of the DCP was hydrolysed. Incubation of the soil solution at 35°C without enzyme increased MRP to 44% of the TDP, reflecting native enzyme activity. Soil solution containing a higher concentration of TDP (1.27 mg dm–3) was also obtained. The distribution of MRP, DOP and DCP fractions was similar but acid phosphatase hydrolysed a greater proportion of the P and MRP increased to 64% of the TDP and at least 40% of the DCP was hydrolysed. The results of hydrolysis with phytase were similar to those with acid phosphatase. The protection of part of the DOP or DCP fraction from hydrolysis was likely caused by occlusion within colloids or the existence of P compounds unlike those of the model substrates.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s003740050229
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    Electronic Resource
    Effect of phosphate rock, lime and cellulose on soil microbial biomass in acidic forest soil and its significance in carbon cycling (1997)
    Springer
    Biology and fertility of soils 24 (1997), S. 329-334 
    Details
    ISSN: 1432-0789
    Keywords: Key words Acidic forest soil ; Phosphorus ; Coal combustion by-product ; Carbon cycling ; Cellulose ; Microbial biomass ; Liming
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Geosciences , Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Abstract Phosphate rock (PR), limestone, coal combustion by-product (CCBP) high in Ca and high organic manures are potential amendments for increasing agricultural production in the acidic soils of the Appalachian region. The objective of this study was to examine effects of PR, CCBP and cellulose addition on soil microbial biomass in an acidic soil based on the measurement of soil microbial biomass P (P mic) and on the mineralization of organic matter. Application of PR alone or in combination with CCBP increased P mic. The P mic was far less when the soil received PR in combination with limestone than with PR application alone or PR in combination with CCBP. Either CCBP or limestone application alone considerably decreased P mic in the soil due to reduced P solubility. Cellulose addition alone did not increase P mic, but P mic was significantly increased when the soil was amended with cellulose in combination with PR. The decomposition of added cellulose was very slow in the soil without PR amendment. However, mineralization of both native organic matter and added cellulose was enhanced by PR application. Mineralization of organic matter was less when the soil was amended with PR in combination with high rates of CCBP (〉 2.5%) because PR dissolution varied inversely with amount of CCBP addition. Overall, CCBP had no detrimental effect on soil microbial biomass at low application rates, although, like limestone, CCBP at a high rate may decrease P mic in P-deficient soils through its influence on increased soil pH and decreased P bioavailability in the soil. Application of PR to an acidic soil considerably enhanced the microbial activity, thereby promoting the cycling of carbon and other nutrients.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s003740050252
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  • 44
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    Electronic Resource
    Mechanisms for the increase in phosphorus uptake of waterlogged plants: soil phosphorus availability, root morphology and uptake kinetics (1997)
    Springer
    Oecologia 112 (1997), S. 150-155 
    Details
    ISSN: 1432-1939
    Keywords: Key words Grasslands ; Mineral nutrition ; Allocation ; Phosphorus ; Adaptations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Waterlogging frequently reduces plant biomass allocation to roots. This response may result in a variety of alterations in mineral nutrition, which range from a proportional lowering of whole-plant nutrient concentration as a result of unchanged uptake per unit of root biomass, to a maintenance of nutrient concentration by means of an increase in uptake per unit of root biomass. The first objective of this paper was to test these two alternative hypothetical responses. In a pot experiment, we evaluated how plant P concentration of Paspalum dilatatum, (a waterlogging-tolerant grass from the Flooding Pampa, Argentina) was affected by waterlogging and P supply and how this related to changes in root-shoot ratio. Under both soil P levels waterlogging reduced root-shoot ratios, but did not reduce P concentration. Thus, uptake of P per unit of root biomass increased under waterlogging. Our second objective was to test three non-exclusive hypotheses about potential mechanisms for this increase in P uptake. We hypothesized that the greater P uptake per unit of root biomass was a consequence of: (1) an increase in soil P availability induced by waterlogging; (2) a change in root morphology, and/or (3) an increase in the intrinsic uptake capacity of each unit of root biomass. To test these hypotheses we evaluated (1) changes in P availability induced by waterlogging; (2) specific root length of waterlogged and control plants, and (3) P uptake kinetics in excised roots from waterlogged and control plants. The results supported the three hypotheses. Soil P avail-ability was higher during waterlogging periods, roots of waterlogged plants showed a morphology more favorable to nutrient uptake (finer roots) and these roots showed a higher physiological capacity to absorb P. The results suggest that both soil and plant mechanisms contributed to compensate, in terms of P nutrition, for the reduction in allocation to root growth. The rapid transformation of the P uptake system is likely an advantage for plants inhabiting frequently flooded environments with low P fertility, like the Flooding Pampa. This advantage would be one of the reasons for the increased relative abundance of P. dilatatum in the community after waterlogging periods.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s004420050294
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  • 45
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    Electronic Resource
    Site fertility and leaf nutrients of sympatric evergreen and deciduous species of Quercus in central coastal California (1997)
    Springer
    Plant ecology 130 (1997), S. 121-131 
    Details
    ISSN: 1573-5052
    Keywords: Deciduous ; Evergreen ; Leaf nutrient levels ; Nitrogen ; Phosphorus ; Quercus ; Soil fertility
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Leaf and soil nutrient levels interact with and may each influence the other. We hypothesize that to the extent soil fertility influences the nutritional state of trees, soil fertility should correlate with summer leaf nutrient levels, whereas to the extent that trees influence soil nutrient levels, the quality of leaf litterfall should correlate with soil fertility. We examined these correlations for five sympatric oak species (genus Quercus) in central coastal California. Soil fertility, including both nitrogen and especially phosphorus, correlated significantly with summer leaf nutrient levels. In contrast, phosphorus, but not nitrogen, in the leaf litterfall correlated positively with soil nutrients. These results suggest that soil nitrogen and phosphorus influence tree nutrient levels and that leaf phosphorus, but not leaf nitrogen, influence soil fertility under the trees. Feedback between the soil and the tree for phosphorus, but not nitrogen, is apparently significant and caused by species-specific differences in leaf quality and not by litterfall quality differences within a species. We also compared functional differences between the evergreen and deciduous oak species at our study site. There were no differences in soil nitrogen and only small differences for soil phosphorus between the phenological types. Differences in leaf nutrient concentration were much more pronounced, with the evergreen species having substantially lower levels of both nitrogen and phosphorus. Evergreen species conserved more phosphorus, but not more nitrogen, than the deciduous species, but there was no consistent relationship between retranslocation and either soil nitrogen or phosphorus. These results do not support the hypothesis that evergreenness is an adaptation to low soil fertility in this system.
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    URL: http://dx.doi.org/10.1023/A:1009798327200
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  • 46
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    Electronic Resource
    Soil nutrient dynamics and community boundaries in the Fynbos vegetation of South Africa (1997)
    Springer
    Plant ecology 130 (1997), S. 143-153 
    Details
    ISSN: 1573-5052
    Keywords: Community boundaries ; Fynbos ; Nitrogen ; Phosphorus ; Soils
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The relationship between changes in soil nutrient characteristics and fynbos community boundaries was investigated near Cape Agulhas, South Africa. Soil characteristics relating to total nutrient content (pH, total N and total P, organic carbon, and various cations) were assessed at sites along three transects crossing the boundaries between five plant communities. Dynamics of available N and P in soils of three communities were studied in the field over one year, using ion-exchange resins. There was a wide range in the degree of change in soil nutrient content across different community boundaries. The characteristics that varied most were pH, total N, Ca and total P. Differences in available nutrients among soils indicated that the communities in this landscape were associated with a mosaic of N and P availability. It is proposed that spatial variation in soil nutrient availability rather than total soil nutrient contents may be important in explaining landscape-level species distributions and community composition in nutrient-poor mediterranean-climate ecosystems.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1009742225383
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    Fe and Al Sedimentation and their Importance as Carriers for P, N and C in a Large Humic Lake in Northern Sweden (1997)
    Springer
    Water, air & soil pollution 99 (1997), S. 283-295 
    Details
    ISSN: 1573-2932
    Keywords: Sedimentation ; Iron ; Aluminum ; Fractionation ; Organic material ; Phosphorus ; Humic lakes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract The sedimentation of organic, amorphous oxides, crystalline oxides and crystalline silicate species of Fe and Al was investigated in humic Lake Örträsket. The covariation with C, N and P sedimentation also was studied. The results showed a strong temporal variation in the occurrence of different Fe species. During high discharge, such as in spring, Fe mostly occurred as crystalline Fe-silicate species, while the amorphous form dominated at other times of the year. Al generally sedimented as crystalline Al-silicate species (95%). Amorphous Fe species showed a strong relation with organic C and N, suggesting an association between organic material and amorphous Fe oxides. P was not as strongly related to amorphous Fe, probably as a result of apatite or clay bound-P species sedimentation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1018342029221
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  • 48
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    Fe and Al sedimentation and their importance as carriers for P, N and C in a large humic Lake in Northern Sweden (1997)
    Springer
    Water, air & soil pollution 99 (1997), S. 283-295 
    Details
    ISSN: 1573-2932
    Keywords: Sedimentation ; Iron ; Aluminum ; Fractionation ; Organic material ; Phosphorus ; Humic lakes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract The sedimentation of organic, amorphous oxides, crystalline oxides and crystalline silicate species of Fe and Al was investigated in humic Lake Örträsket. The covariation with C, N and P sedimentation also was studied. The results showed a strong temporal variation in the occurrence of different Fe species. During high discharge, such as in spring. Fe mostly occurred as crystalline Fe-silicate species, while the amorphous form dominated at other times of the year. Al generally sedimented as crystalline AI-silicate species (95%). Amorphous Fe species showed a strong relation with organic C and N, suggesting an association between organic material and amorphous Fe oxides. P was not as strongly related to amorphous Fe, probably as a result of apatite or clay bound-P species sedimentation.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02406868
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  • 49
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    Hydrogen Bonding and Conformational Analysis of Chelate-Stabilized Alkoxopalladium(II) Complexes Derived from Amino Alcohol Ligands (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 35-44 
    Details
    ISSN: 0009-2940
    Keywords: Alkoxopalladium(II) ; Conformational analysis ; Hydrogen bonding ; Two-dimensional and cage structures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of palladium acetate with two equivalents of di- and triethanolamines RN(CH2CH2OH)2 in the presence of a base affords the new chelate-stabilized alkoxo Pd(II) complexes [Pd(OCH2CH2N(R)CH2CH2OH)2] [R = Me (1), Et (2), n-Bu (3), benzyl (4) or CH2CH2OH (5)]. These N,O-ligated complexes are isolated in high yield as yellow, crystalline solids and are thermally stable despite the presence of several β-hydrogen atoms in the ligand system. Both complexes possess a square-planar palladium coordination geometry with the two oxygen atoms positioned mutually trans. The most notable difference in the molecular structures is that 1 forms a two dimensional network of intermolecular O-H≡O hydrogen bonds, whereas 5 forms intramolecular O-H⃛O hydrogen bonds, which cage the palladium center. In solution 1-4 exist as a diastereoisomeric mixture (a racemic enantiomeric pair SNSN, RNRN and a mesomeric form RNSN) in a 1:1 molar ratio, and this ratio is independent of temperature in nonalcoholic solvents, When complexes 1-4 are dissolved in protic solvents (e.g. MeOH) the diastereomeric excess is temperature-dependent due to an exchange process between the meso diastereoisomer and the (racemic) enantiomeric pair. Thermodynamic parameters for this process in a mixture of MeOH-toluene have been determined with NMR and show this process to be influenced by the steric nature of the alkyl substituent (R) on nitrogen. A conformational analysis based on 1H-NMR coupling constants within the N,O-chelate ring of complexes 1-4 provides details on the solution structure of the ring in both diastereoisomers.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300106
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  • 50
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    Synthesis of Functionalized Carbamates through a Palladium-Catalyzed Reductive Carbonylation of Substituted Nitrobenzenes (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 13-22 
    Details
    ISSN: 0009-2940
    Keywords: Carbamates ; Catalysis ; Substituted nitrobenzenes ; Palladium ; Reductive carbonylation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The palladium-catalyzed reductive carbonylation of ortho and para-substituted nitrobenzenes has proven to be an attractive route for the synthesis of functionalized carbamates. For the Pd(1, 10-phenanthroline)2(triflate)2 catalyst system, the scope of the reaction has been studied. Substrates with electron-donating substituents at the para position were found to decrease the catalytic activity, most probably as a result of their relatively low oxidizing capacity. the selectivity towards the desired carbamate, however, was increased for these substrates. Under the influence of electron-withdrawing substituents the azoxybenzene and azobenzene derivatives became important side products. Introduction of large steric hindrance at the ortho position of the nitro substrates gave rise to an interesting side reaction, viz. methoxylation of the aromatic ring. The methoxylation reaction appeared to occur on an intermediate species in the catalytic cycle. Several functionalities have shown to be resistant to the reaction conditions required for the conversion ot the nitro group. Especially with 4-nitrobenzoic acid, an extremely high activity and selectivity was found, thus yielding a very convenient synthesis for N-protected amines containing carboxylic acid function.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300104
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  • 51
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    Dimeric Silver(I) Complexes of Some Isothiazole-Based LigandsDedicated to Prof. Dr. Rolf Gleiter on the occasion of this 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 95-100 
    Details
    ISSN: 0009-2940
    Keywords: Isothiazole complexes ; Dinuclear silver(I) complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of isothiazole-based potential ligands bearing substituents with additional donor sites in the 5-position of the heterocycle was synthesized [3-Me-5-R-C3HNS; R = CH=N(CH2)2py (1), CH=NCH2py (2), CH2N(CH2CH2NEt2)2 (4), (CH2)2SMe (5)]. Upon reaction with AgO3SCF3 they formed complexes [(1)AgOSO2CF3]2 (6), [(2)AgOSO2CF3]2 (7), [(4)Ag]2+2(O3SCF-3)2 (8) and [(5)AgOSO2CF3]2 (9), respectively. 6, 8 and 9 were shown by X-ray structural analyses to consist of dimeric units L2Ag2+2, either discrete (8), coordinated by terminal CF3SO-3 units (6). In 8 and 9 the isothiazole moiety is bonded to the metal center via the ring-N. The coordination potential of the isothiazole heterocycle is discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300115
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  • 52
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    Synthesis and Structure of Binuclear Single-Bridged Bis[(phosphane)gold(I)]halogenonium Complexes (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 115-118 
    Details
    ISSN: 0009-2940
    Keywords: Gold complexes ; Bromonium complex ; Halogenonium complex ; Halogen, two-coordinate ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of (R3P)AuX (X = Cl, Br, I) with [(R3P)Au]+ BF-4 obtained from (R3P)AuCl and AgBF4 in tetrahydrofuran, lead to cationic binuclear gold(I) complexes of the general formula ([(R3P)Au]2X}+ BF-4. A number of chloro- (R = Ph, o-Tol, Mes, Bzl, Et), bromo- (R = Ph, o-Tol, Mes) and iodo-bridged (R = Ph, Mes) complexes of this type have been isolated and identified on the basis of their analytical and spectroscopic data. The crystal structure of bis[(triphenylphosphane)gold(I)]bromonium tetrafluoroborate was determined by single-crystal X-ray diffraction. The cations contain two-coordinate bromine atoms with an Au-Br-Au angle of 96.83(3)°.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300119
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  • 53
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    A Specific Route to Enantiomerically Pure Asymmetric (η6-Arene)(η4-1,5-cyclooctadiene)Ru(0) ComplexesDedicated to Professor Rolf Gleiter on the occassion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 123-130 
    Details
    ISSN: 0009-2940
    Keywords: Arene complexes ; Ruthenium compounds ; Electrophilic substitution ; Lithiation ; Catalysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Chiral or achiral (arene)(COD)Ru complexes can be made by replacing the η6-ligands of (η4-1,5-COD)(η6-1,3,5-cyclooctatriene)Ru (1) or (η4-1,5-COD)(η6-naphthalene)Ru (2) by a suitable arene. This well known reaction has been extended to mono- and dibromoarenes and we report a novel route to substituted (arene)(COD)Ru species, utilizing (bromoarene)-(COD)Ru as starting materials. These facilitate a rapid bromine-lithium exchange reaction with nBuLi at low temperatures and the lithiated species react readily with alkyl chloroformates as electrophiles. By using chiral electrophiles [alkyl = (-)-menthyl] enantiomerically pure or diastereomeric complexes containing CO2R* groups are formed, depending on the symmetry of the original complex. A diastereomeric 1:1 mixture was separated by recrystallization. All (arene)-(COD)Ru complexes tested so far are useful as catalysts for the hydrogenation of simple alkenes at room temperature.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300121
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  • 54
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    Recent Advances in C-F Bond Activation (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 145-154 
    Details
    ISSN: 0009-2940
    Keywords: Fluorocarbons ; C-F bond activation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The main reaction pathways which lead to the breaking of C-F bonds in perfluoroalkanes and -arenes are discussed. Emphasis is placed on recent developments and on the mechanistic patterns that emerge.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300203
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    Metal Atoms in the Synthesis of Metal Clusters, VIII.On the Reaction of Sterically Demanding Cyclopentadiene Ligands with Cobalt Atoms: Synthesis, Crystal Structure, Spectroscopic Behavior, and Reactivity of Di-, Tri- and Tetranuclear Hydrido Clusters of CobaltDedicated to Professor IV Siehert on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 161-170 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The metal-vapor reactions of Co atoms with 1,3-tBu2CpH (1a), 1,3-tBu2CpH (1a), 1,2,4-tBu3CpH (1b) and EtMe4CpH (1c) are described. With 1a the two mononuclear complexes [(η5-tBu2Cp) (η4-tBu2-1,3-cyclopentadiene)Co] (2a) and [(η5-tBu2Cp)2Co] (3a) were isolated, together with the dinuclear cobalt cluster [{(η5-tBu2Cp)Co}2H3] (4a) and trace amounts of the tetranuclear cluster [{(η5-tBu2Cp)CoH}4] (5a). The molecular structures of 3a and 4a were determined by X-ray diffraction. Reaction of 1b with Co atoms afforded a single product, the dinuclear cluster [{(η5-tBu3Cp)Co}2H3] (4b), whose molecular structure was determined by single-crystal X-ray diffraction. Both, 4a and 4b exhibit extremely short Co-Co distances [2.244(1) (4a) and 2.242(1) Å (4b)], as found for the Me5Cp analog [{(η5-Me5Cp)Co}2H3] (4c). Reaction of an isomeric mixture of Me4EtCpH (1c) with Co atoms furnished the mononuclear sandwich [ (η5-Me4EtCp)(η4-Me4Et-1,3- cyclopentadiene)Co] (2b), the trinuclear hydridocobalt cluster [{(η5-Me4EtCp)Co}3H4] (6a) and the tetranuclear hydridocobalt cluster [{(η5-Me4EtCp)Co}4H4] (5c). The molecular structure of 5c was determined by X-ray crystallography and revealed a tetrahedral arrangement of the cobalt atoms. The electrochemical behavior of the dinuclear complexes 4a-4c was studied by cyclic voltammetry. Reversible redox couples were found for all three compounds, with a correlation between the degree of alkyl substitution and their respective cathodic shifts. Compounds 4a and 4b react with CO to yield the mononuclear and dinuclear complexes [ (η5- CpR)Co(CO)2] (R=1,3-tBu2, 1,2,4-tBu3) (7a and 7b) as well as [{(η5-CpR)CO}2(CO)2] (8a and 8b). Reaction of the trinuclear hydridocobalt cluster 6a and its Me5Cp analog 6b with AgBF4 in the presence of PEt3 yielded the heteronuclear clusters [{η5-Me4CPR)Co}3AgP(Et)3H4]+[BF4]- (R=Et, Me) (9a and 9b). 9a was structurally characterized by X-ray crystallography.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300205
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  • 56
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    Generation and Synthetic Application of Metallated Methyl Isopropenyl Ether, A Substitute for Acetone Enolate (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 45-48 
    Details
    ISSN: 0009-2940
    Keywords: Metallated methyl isopropenyl ether ; Tetrahydrofurans ; 1-Oxabicyclo[4.3.0]heptanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methyl isopropenyl ether (1) has been metallated at low temperature with a 1:1 molar mixture of n-BuLi/t-BuOK in THF-hexane, and subsequently functionalized with a variety of electrophilic reagents. At temperatures higher than - 30°C, the metallated methyl isopropenyl ether (2) decomposes with formation of allene. When the suspension of 2 is allowed to warm up to room temperature in the presence of an additional equivalent of n-BuLi, the intermediary allene is converted into 1-propynyllithium (2c), which reacts with propylthiocyanate to give 1-propylthio-1-propyne (4). Some of the functionalization products were subjected to acidic hydrolysis affording the expected methyl ketones.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300107
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  • 57
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    Asymmetric Catalysis, 105Part 104: Ref.. Stereoselective Hydrogenation of Folic Acid with Immobilized Optically Active Rhodium(I)/Diphosphane Catalysts (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 55-62 
    Details
    ISSN: 0009-2940
    Keywords: Diastereoselective hydrogenation ; Folic acid ; Immobilized optically active rhodium(I)/diphosphane catalysts ; Leucovorin ; HPLC analysis of 5-formyltetrahydrofolic acid derivatives ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: For the hydrogenation of the C=N bonds in the pyrazine ring of the vitamin folic acid (1) optically active rhodium(I)/diphosphane complexes immobilized on supports such as silica gel or Al2O3 were used. The reduction was carried out at 50 bar hydrogen pressure in an aqueous solution buffered to pH 7. Thus, 5,6,7,8-tetrahydrofolic acid (2) was obtained which contains a new asymmetric center at C-6 of the pterine system. Therefore, in combination with the (S) configuration of the natural L-glutamic acid part of the molecule two diastereomers with (6S,S) and (6R,S) configuration arise. The relatively unstable tetrahydrofolic acid (2) was converted into its 5-formyl derivative folinic acid (4) by treatment with methyl formate/formic acid in a 5:1 mixture of DMSO/pyridine. The Ca salt of folinic acid (4) is the widely used drug leucovorin. The diastereomers were separated by silica gel HPLC. To the column bovine serum albumine (BSA) is covalently bound. With optically active rhodium(I)/diphosphane catalysts, immobilized on silica gel supports, a diastereoselectivity of up to 90% could be achieved in the hydrogenation of folic acid (1).
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300109
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  • 58
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    Hexahydro-closo-hexaborane as a Ligand in Coordination Compounds: Syntheses and Crystal Structures of [M2(μ-bis-η3-B6H6)(PPh3)2] )M = Cu, Au) (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 405-408 
    Details
    ISSN: 0009-2940
    Keywords: Hexahydro-closo-hexaborates ; Boron ; Bridging ligands ; NMR spectroscopy ; Gold ; Copper ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By reaction of (PPh3)3 CuCl and PPh3AuCl with [B6H6]2- in organic media, dinuclear complexes are formed containing the hexaborate as a bridging ligand coordinated to the metal centers by opposite B3 facets of the B6 cluster in a trihapto mode. This is verified by single-crystal X-ray structural analysis of the isotypical (Paā) compounds [Cu2μ-bis-η3-B6H6)(PPh3)2] (1) and [Au2(μ-bis-η3-B6H6)(PPh3)2)] (2) which showed the metal centers to be very close to the B3 plane [1.92 (1), 2.10 (2) Å. The 11B NMR spectra of the two compounds feature doublets, at δ= -15.32 in 1 and at -11.51 in 2, which are significantly shifted downfield in comparison to [B6H6]2- (δ= -17.2).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300315
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  • 59
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    Crown Thioether Chemistry: Novel Silver(I) Complexes of 1,3-Dithiole-Annelated 1,4,7-Trithiacyclononane (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 425-429 
    Details
    ISSN: 0009-2940
    Keywords: Silver complexes ; Crown compounds ; Thioethers ; 1,3-Dithioles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The coordination chemistry of two crown thioethers 2,5,8,10,12-pentathiabicyclo[7.3.0]dodeca-1)9)-ene-11-thione (L) and -11-one (L') with Ag1 has been investigated by structural methods. Both thioethers act as tridentate ligands coordinating the silver ion in a trigonal fashion. In the case L, the 11- thione sulfur is coordinated additionally by another silver ion, to yield a polymeric chain with a distorted-tetrahedral geometry about the metal ion. Despite differing only in its carbonyl chalcogen, L' forms six-coordinated, monomeric complexes.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300319
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    Unsymmetric Dinucleating Ligands for Metallobiosite Modelling (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 433-442 
    Details
    ISSN: 0009-2940
    Keywords: Metallobiosites ; Metalloproteins ; Metalloenzymes ; Dinucleating ligands ; Transition metals ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Awareness of the asymmetric nature of numerous dinuclear metallobiosites and of the ability of the individual metal ions to have quite distinct roles in the functioning of the metalloenzyme concerned has led to a search for carefully designed unsymmetric dinucleating ligands that will give dinuclear complexes capable of acting as models for the metallobiosites. This review surveys progress made in the design and synthesis of complexes capable of serving as models for donor atom, coordination number and geometric asymmetries found at dinuclear metal centres.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300402
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    Chemie polyfunktioneller Moleküle, 125Part 124: Ref. Synthese und Kristallstruktur von N,N,N′,N“,N-Pentamethyl-diethylentriamin-cokoordiniertem Kalium-bis(diphenylphosphanyl)amidHerrn Prof. Dr. Gerhard Herberich zum 60. Geburtstage gewidmet. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 141-144 
    Details
    ISSN: 0009-2940
    Keywords: Alkali metal organophosphanylamide ; Carbon-potassium bonding ; Phosphazane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The metalation of bis(diphenylphosphanyl)amine [HN-(PPh2)2,1 with KOtBu at 95°C in toluene affords a pale yellow precipitate of potassium bis(diphenylphosphanyl)amide (3a). On addition of liquid N,N,N′,N“,N“-pentamethyldiethylenetriamine (PMDTA, 4) the precipitate dissolves in toluene at 115°C to give a yellow solution, from which yellow-green blocks of [(Ph2P)2NK·PMDTA] (3b) are obtained. X-ray analysis reveals that the coordination sphere of potassium consists of the chelating triamine ligand and [N(PPh2)2]- as N-donor as well as η1 and η2 C-donor with two phenyl fragments. No phosphorus coordination of [N(PPh2)2]- is observed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300124
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    Organophosphorus Compounds, 114. Tetracyclic Phosphorus-Aluminium-Carbon Compounds - Synthesis by Cooligomerization of Kinetically Stabilized Phosphaalkynes with Trialkylaluminium CompoundsDedicated to Professor Michael Hanack on the occasion of his 65th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 255-259 
    Details
    ISSN: 0009-2940
    Keywords: Phosphaalkynes ; Triorganoaluminium compounds ; Cooligomerization ; Cage compounds ; Aluminium compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When the trialkylaluminium reagents 5 are allowed to react with phosphaalkynes 4 in n-pentane, a highly selective phosphaalkyne cyclotrimerization with incorporation of two organometallic units occurs (→ 6). The tetracyclooctane derivatives 6a-e represent the first examples of phosphorus-aluminium-carbon cage compounds. The polycyclic products 6 are able to function as ligands in transition-metal complexes (→ 7), which is illustrated by the reactions of 6b, c with nonacarbonyldiiron and pentacarbonyl(tetrahydrofuran)tungsten, respectively.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300219
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    On the Ligating Properties of Sulfonate and Perchlorate Anions Towards Zinc (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 283-289 
    Details
    ISSN: 0009-2940
    Keywords: Zinc ; Sulfonate ligands ; Perchlorates ; Coordination modes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Attempts are reported to incorporate sulfonate and perchlorate anions as ligands in zinc complexes of tripodal ligands. Using tris(benzimidazolylmethyl)amine (BIMA) only the aqua complexes [ (BIMA)Zn-OH2](RSO3)(ClO4) and [(BIMA)Zn-OH2](RSO3)2(R=CH3, CF3, p-tolyl) were accessible. Using substituted pyrazolylborates (Tp*), the same three sulfonate anions were found to be ligands in the complexes Tp*Zn-OSO2R. Spectroscopic evidence for perchlorate coordination in Tp*ZnClO4 · 2 DMSO conflicts with crystallograpic evidence against it in Tp*ZnClO4 · pyridine. The crystal structures of [(BIMA)Zn-OH2](CH3SO3)2, TpCum,MeZn-OS02CH3, TPtBu,MeZn-OSO2C6H4-p-CH3, and [TpCum,MeZn · NC5H5]ClO4 were determined.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300223
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    Multiple Bonds Between Main-Group Elements and Transition Metals, CLXIV. Alkylrhenium(VI) Oxides-Synthesis and Characterization (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 295-298 
    Details
    ISSN: 0009-2940
    Keywords: Rhenium ; Oxides ; Alkyl ligands ; Dirhenium compounds ; Metal-metal interactions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Most alkylrhenium(VII) oxides, e.g. ((cyclo)-C3H5)Re03 (2) are rather sensitive to temperature and moisture with the prominent exception of methyltrioxorhenium (1). The corresponding alkylrhenium(VI) oxides of formula [RR′(O)- Re(μ-O)]2 [R=R′=(cyclo)-C3H5 (3), iPr (4); R=CH3, R′=C2H5 (5), R=CH3, R′=iPr (6)] are much more stable in this regard. They can be handled in air at room temperature. They were synthesized from Re207 and dialkylzinc precursors, fully characterized and are available in much higher yields than their ReVII congeners. Mixed tetraalkyltetraoxodirhenium(VI) complexes (R # R′) synthesized from 1 and dialkylzinc compounds form as a mixture of cis/trans isomers. They are oily liquids at room temperature. The Re=O and Re-Re stretching force constants as a measure of the bond strengths, were determined from IR and Raman data.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19971300225
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    Hydroxy- and Carboxy-Substituted Allylsilanes: A Simple and Stereoselective Method of Preparation (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 335-340 
    Details
    ISSN: 0009-2940
    Keywords: Allylsilanes ; Superbases ; Metalations ; Stereoselectivity ; Cyclizations ; Silicon ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When treated with two equivalents of a butyllithium/potassium tert-butoxide mixture, terminal olefins carrying unprotected hydroxy or carboxy groups generate allylmetal intermediates which can be trapped with chlorotrimethylsilane to afford functionalized (Z)-2-alkenyltrimethylsilanes. One equivalent of the superbasic reagent suffices if the unsaturated alcohols are first protected as acetals before being subjected to the metalation/silylation/hydrolysis sequence.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300306
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    Preparation, Properties, and Reactions, of Metal-Containing Heterocycles, XCVIPart XCV: E. Lindner, E. Bosch, R. Fawzi, M. Steimann, H.A. Mayer, K. Gierling, Chem. Ber. 1996, 129, 945-951.. Mono-, Di- and Trinuclear Metallacycloalkanes of the Iron-TriadDedicated to Professor Wolfgang Beck on the occasion of his 65th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 347-356 
    Details
    ISSN: 0009-2940
    Keywords: Metallacycloalkanes ; Metallacycloalkenes ; Osmium ; Iron ; Cyclic ketones ; Metallacycles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of the bis(triflates) [F3CSO3-(CH)m-O3SCF3] [m = 5-10, 12, 14, 16 (1a-i) with Na2[Os(CO)4] in dimethyl either affords the osmacycloalkanes 2a, 2b and 2f-i (m = 5, 6, 10, 12, 14, 16), diosmacycloalkanes 3a-i (m = 5-10, 12, 14, 16), and triosmacycloalkanes 4a-i (m = 5-10, 12, 14, 16). The structure of 3f was investigated by an X-ray structural analysis. This 22-membered disomacycle crystallizes in the space group Pā with Z = 1. If the unsaturated cis-4-octen-1,8-diyl bis(trifluoromethanesulfonate) (5) is treated with Na2[Os(CO)4] the diosmacyclooctadeca-5,14-diene 6 is obtained. By treating the bis(triflates) 1a, b with Na2[Fe(CO)4] the corresponding ferracycloalkanes are formed only in situ. Insertion of carbon monoxide into the M-C σ bonds leads to the cyclic ketones 7a, d and to the diketone 8d.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300308
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    Enantioselective Catalysis, XIIIPart XII: U. Nagel, J. Leipold, Chem. Ber., 1996, 129815-821.. Preparative and Structural Chemistry of Chiral 3-(Diphenylphosphanyl)-pyrrolidiens and Their Palladium(II) Complexes (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 385-398 
    Details
    ISSN: 0009-2940
    Keywords: Pyrrolidinephosphanes ; 3-Hydroxypyrrolidine ; 3-Diphenylphosphanylpyronlidine ; Salt effects ; Polymorphism ; Homogeneous catalysis ; Palladium ; Asymmetric catalysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The preparation of both enantiomers of 3-diphenylphosphanulpyrrolidiine (2) and several N-substituted derivatives together with two PdIi complexes of this ligand is reported. Form L-malic acid and L-hydroxyproline both enantiomers of 3-hydroxypyrrolidine are prepared without any problems due to epimerization. KPPh2 in the presence of LiCl is shown to be the most effective reagent for the synthesis of 2. The reported X-ray structure determination sof Pdl2 complexes show a rather rigid bicyclic hetero-norbornane skeleton. The flexibility of the other parts of the molecules is obvious in several polymorphs revealed by this method. This polymorphism is additionally investigated by a 31P-CP-MAS study. From solution 1-, 13C- and 31P-NMR studies it is concluded that the bicyclic hetero-norbornane skeleton is retained in solution.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300313
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    Reactions of Silicon-Silicon Bonds, VIFor part V, see ref.[1].. Reductive Trichloroslilylation Reactions Leading to Alkyl- and Dialkylaminobis(trichlorosilyl)phosphanesDedicated to Professor Walter Siebert on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 377-384 
    Details
    ISSN: 0009-2940
    Keywords: Trichlorosilylation ; Dichlorophosphanes ; Silylphosphanes ; Amino(silyl)phosphanes ; Silicon /Reductions ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reactions of hexachlorodisilane and of trichlorosilane/triethylamine with alkyl-and dialkylaminodichlorophosphanes RPCl2 1a-i [R = iPr: a; (Me3Si)2CH: b; R=1-adamantly: c: R=tBu: d; R=Et2N: e; R=iPr2M: f] furnish bis(trichlorosilyl)-phosphanes RP(SiCl3)2 3a-f. However, when less bulky substituents are attached to the phosphorus atom, so that there is little steric crowding, the double reductive silylations leading from 1 to 3 are accompanied by side reactions and decomposition of 3. Therefore, only 3b, 3c, 3d, and 3f wre isolated in a pure state. These compounds are more readily prepared by the; trichlorosilane/triethylamine method. 1H-, 31P- and 29Si-Nmr spectra confirm their constitution. The structure of solid 3f, the first aminobis(trichlorosilyl)phosphane, was determined by X-ray crystallography. 3f contains a phosphorus atom in a pyramidal environment surrounded by two silicon atoms and a planar nitrogen atom of the diisopropylamino group.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300312
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    Formation of the Digallium Compound [(C5C6)2N3](R)Ga-Ga(R)[N3(C6H5)2] with Two Bis(trimethylsilyl)methyl Groups and Two Terminal Chelating Diphenyltriazenido Ligands (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 417-420 
    Details
    ISSN: 0009-2940
    Keywords: Gallium ; Low-valent compounds ; Gallium-gallium bond ; Terminal triphenytriazenido ligand ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetrakis[bis(trimethylsilyl)methyl]digallane (4) 1 reacts with 1,3-diphenyltriazene to yield two compounds, which were both characterized by a crystal structure determination. The gallium-gallium bond is retained in the yellow derivate [(H5C6)2N3](R)Ga-Ga(R)[N3(C6H5)2 2 [R = CH(SiMe3)2], which is formed by a ligand exchange reaction and shows two terminal chelating triazenido ligands besides two bis(trimethylsilyl)methyl groups; the Ga—Ga bond length is 245.79(6) pm. The second product is the orange dialkyl(diphenyltriazenido)gallium derivative R2Ga[N3(C6H5)2] 3, where the triazene has reacted as an oxidant by the cleavage of the Ga—Ga bond and probably by release of elemental hydrogen.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300317
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    The Electronic Structure of [Te15Br4][MoOBr4]2 and Some General Aspects of Bonding in “Classical” and Hypervalent Tellurium Halides (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 463-472 
    Details
    ISSN: 0009-2940
    Keywords: Hypervalent compounds ; Tellurium ; Polycations ; Molecular Orbital Theory ; Band structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Approximate MO and band structure calculation are used to analyze the bonding in the recently synthesized paramagnetic, semiconducting phase [Te15Br4]2+. The [Te15Br4]2+ chains are very similar to those in the tellurium subhalide Te2Br. The electronic structure and bonding within these chains is analysed and the possibility of hypervalency in both [Te15Br4][MoOBr4]2 and Te2Br is discussed. The bonding in the classically hypervalent molecule TeBr42- and a model Te3Br24- is compared to that of the infinite system. Our calculations indicate that both [Te15Br4][MoOBr4]2 and Te2Br contain weakly hypervalent Te atoms and that the interesting electronic properties of [Te15Br4][MoOBr4]2 arise within the distinct sublattices, which do not interact significantly.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300405
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    Heterobimetallic Complexes with a Propynylidene C3-Bridge: General Synthetic Routes to Bimetallic Ethynylcarbene Complexes (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 479-488 
    Details
    ISSN: 0009-2940
    Keywords: Heterobimetallic complexes ; Carbene complexes ; Alkynes ; Coupling reaction ; Bridging ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sequential reaction of the dimethylamino(trimethylsilylethylnyl)carbene complexes [(CO)5M'=C(NMe2)C≡CSiMe3] [M' = W (1a)] with KF/THFMeOH, nBuLi and transition metal halides, [XMLn], affords heterobimetallic propynyliden complexes of the type [(CO)5M'=C(N-Me2)C≡CMLn] [MLn = Ni(PPh3) Cp (4a, b). Ni(PMe2Ph)2- {Mes) (Mes=2,4,6-C6H2Me3) (5a), Rh(CO)(PPh3)2 (6a), Fe(CO)2Cp (7a,b)]. In contrast, reaction of 1a with MeLi · LiBr and [IFe(CO)2Cp] yields the novel N-metallated complex [(CO)5W=C{N(ME)Fe(CO)2Cp}C≡CSiMe3] (8a). The complexes [(CO)5M'=C(NMe2)C≡CMLn=Fe(CO)2Cp (7a, b), Ru(CO)2Cp (10a,b), Ru(CO)(PPh3)Cp (11a), Mn(CO)5 (12a), Re(CO)5 (13a)] are accessible by Pd-catalyzed coupling of the C-stannylated carbene complexes [(CO)5M'=C-(NMe2)C≡CSnBu3] (9a, b) with [XMLn]. The related monomethylaminocarbene complexes [(CO)5M'=C(NHMe)C≡ CSnBu3] (16a, b), obtained by stannylation of [(C))5M'=C(NHMe)C=CH] (15a, B) with Bu3SnNEt2, react with [IFe(CO)2Cp] to give the bimetallic complexes [(CO)5M'=C(NHMe)C≡CFe(CO)2Cp] (17a, b). The complexes 4a, 5a, 7a and 10a were characterized by X-ray structural analysis. The spectroscopic and structural data suggest that the two metal centers in 4-7, 10-13, and 17 interact only weakly.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300407
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    Synthesis and Molecular Structure of a Rhenium Complex Derived from 8a-Amino-6-methyl-ergolineDedicated to Professor Roland Mayer on the occasion of his 70th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 839-841 
    Details
    ISSN: 0009-2940
    Keywords: Rhenium ; Technetium ; 8a-Amino-6-methyl-ergoline ; Chelates ; Structure elucidation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Current research in radiopharmaceutical chemistry is aimed at the design of technetium-based receptor-binding radiotracers because of the excellent nuclide properties of the isotope 99mTc. Tc tracers and the corresponding complexes of rhenium, as the inactive surrogate of Tc, are required to imitate organic agonists or antagonists of the receptor. We have started studies with ergolines, which are known to be dopamine substitutes. The present report deals with the functionalization of 8α-amino-6-methyl-ergoline (2) with a 2-mercaptoacetyl group, and the subsequent synthesis of the first rhenium complex containing a pendent ergoline moiety [Re- O(SSS)(RS)] (HSSSH = HS-CH2CH2-S-CH2CH2-SH and RSH = 8a-amino-N-(2-mercaptoacetyl)-6-methyl-ergoline) (4). The molecular structure of the rhenium complex was determined by X-ray crystal structure analysis.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300705
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    Aminotroponimines as Ligands for Yttrium and Lanthanide Complexes (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 859-862 
    Details
    ISSN: 0009-2940
    Keywords: Yttrium ; Lanthanum ; Samarium ; Lanthanides ; Aminotroponiminate ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of N-isopropyl-2-(isopropylamino)troponimine, [(i-Pr)2ATI]H, with KH in THF affords [(i-Pr)2ATI]K. This is a useful starting material for the preparation of the mono-, bis- and tris-substituted compounds [[i-Pr)2ATI]YCl2-(THF)2}2, [(i-Pr)2ATI2Y[O(2,6,t-Bu2C6H3)] and [(i-Pr)2-ATI]3Ln (Ln = Y, La, Sm), which can be obtained from ([i-Pr)2ATI]K and LnX3 and LnX3 (X = Cl, I), or Y[O(2,6-t-BuC6H3)]3. All compounds have been characterized by spectroscopic methods. The monosubstituted yttrium complex {[(i-Pr)2ATI]YCl2(THF)2}2 has also been investigated by single crystal X-ray diffraction.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300708
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    C-H Bond Activation of Simple Alkenes with (C5H5)CO Fragments: Preparation, Molecular Structure, and Dynamical Behaviour of Tri- and Tetranuclear Cyclopentadienylcobalt Cluster complexes with μ-Cycloalkyne Ligands (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 593-603 
    Details
    ISSN: 0009-2940
    Keywords: C-H activation ; Alkyne complexes ; Cyclopentadienyl cobalt ; Fluxionality ; Hydrido complexes ; Clusters ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vicinal C-H bonds of the cycloalkenes CnH2n (n = 5-8) were activated upon treatment under mild conditions with reactive sources of the (C5H5)CO fragment. With [C5H5)CO(C2H4)2] (2a), the trinuclear cluster complexes [H2((C5H5)CO)3(μ3-C2(CH2)n-2)] (5a: n = 5; 5c: n = 5d: n = 8) were formed. Using the more reactive [(C5H5)2Co]/K, 5a-5dwere obtained, along with small amounts of the tetranuclear [{(C5H5)CO}4r{μ4-C2(CH2)n-2}] (8a-c: n = 5-7). X-ray structure analyses of 5c, d and 8b, c were performed. A μ-‖ (orμ3-η1:η2:η1) coordination of the cycloalkyne ligands was found in the trinuclear cluster complexes. The tetranuclear 8b, c had the cycloalkynes quadruply bridging (μ4-η1:η2:η2:η1_ a butterfly arrangement of the metal atoms. The acetylenic carbon-carbon bonds are considerably lengthened upon coordination [1.392(4), 1.398(3) å in 5c d; 1.464(8), 1.499(5) Å in 8b, c]. Three dynamic processes - alkyne “walk” on top of the CO3 triangle, μ2-hydride migration, and μ2/μ3-hydride exchange - are operational in the trinuclear 5a-d. Dynamic NMR data for 5a are consistent with a “windshield-wiper” mechanism for the alkyne migration. Hydride exchange is associated with a higher energy barrier, and is probably and independent dynamic process.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300510
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    Organoamido- and Aryloxolanthanoids, 15Part 14: Ref. [1a].. Organometallic Compounds of the Lanthanoids, 116Part 115: Ref. [1b].. Syntheses of Low Coordination Number Divalent Lanthanoid Organoamide Complexes, and the X-ray Crystal Structures of Bis[(N-2,6-diisopropylphenyl)(N-trimethylsilyl)amido]bi(tetrahydrofuran)samarium(II)and -ytterbium(II) (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 409-415 
    Details
    ISSN: 0009-2940
    Keywords: Mercury ; Lanthanides ; Lanthanoid(II) complexes ; (N-2,6-Diisopropylphenyl)(N-trimethylsily)amide complexes ; Bis(trimethylsilyl)amide complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Mercury(II) amide complex Hg[N(SiMe3)(2,6-iPr2C6H3)]2 (1) was prepared by reaction of HgBr2 with Li[N(SiMe3) 2,6-iPr2C6H3)] in diethyl ether solvent. Redox transmetallation reactions of 1 with elemental samarium, europium or ytterbium in THF solvent (THF = tetrahydrofuran), generated the novel divalent complexes Ln[N(SiMe3)(2,6-iPr2C6H3]2(THF)2 with Ln = Sm (2), Eu (3) and Yb (4). 4 was also synthesized by reaction of elemental ytterbium, HgPh2 and HN(SiMe3)(2,6-Me3)2]2(THF)2 [Ln = Sm (5), Yb (6)] by reaction of the metals with HgPh2 and HN(SiMe3)2. Thermal desolvation of 4 under high vacuum gave Yb(N)(SiMe3)2,6-iPr2C6H3)]2 (THF) (7), whereas under identical conditions 6 yielded the solvent-free complex [Yb[N{SiMe3)2]2]2. (8). The new compounds 1-4 and 7 are hydrocarbon soluble and 171Yb-NMR spectra were recorded for 4, 6, 7 and 8. X-ray crystal structure determinations of 2 and 4 revealed four-coordinate, distorted tetrahedral metal environments augmented by weak Ln…ipso-C(aryl) interactions.
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    URL: http://dx.doi.org/10.1002/cber.19971300316
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    Synthesis and Structure of 2,2′ -Boryl-, Germyl-Silyl-, and Stannyl-Substituted 1,1′ -Binaphthyl SystemsDedicated to Professor Hans Paulsen on the occasion of his 75th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 923-932 
    Details
    ISSN: 0009-2940
    Keywords: Biaryls ; Boron ; Chirality ; Cooperative Effects ; Lewis acids ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A number of Lewis acid binaphthyl systems, substituted in 2-or 2,2′-position, are synthesized by lithiation of 2,2′-dibromo-1,l ′-binaphthyl (5), followed by addition of various electrophiles. Stepwise lithiation and subsequent borylation with trimethyl borate leads to the bromoboronic acid 6, which can be stabilized by esterification with pinacol giving 7. By increasing the reaction mixture to 2 equiv. of n-butyllithium and 2 equiv. of methyl borate the path to the binaphthylmonoboronic acid ester 9 is opened up. A further increase in the quantity of electrophile also leads to the binaphthylbisboronic acid ester 12. The 2,2′-disubstituted silyl, germyl, and stannyl derivatives 13a-15a are accessible in good yields. Treatment with boron halides leads exclusively to methyl/halogen exchange, giving the bidentate Lewis acids 13b-15b, the former of which can be bridged by oxygen.Only in case of the bis(tributylstannyl)binaphthyl 16a does ipso substitution occur in the presence of boron trichloride, giving the bis(dichloroboryl)-substituted binaphthyl 16b which can then be hydrolysed to 11. The structures of the majority of the compounds were investigated by X-ray diffraction. In case of the 2,2′-disubstituted compounds 13a-15a the naphthyl groups are orientated perpendicular to each other. The intra- and intermolecular interactions are dominated by this binaphthyl system. In case of the oxygenbridged compounds 13c and 14c the angle between the naphthyl planes decreases to about 70°. This also has an effect on the packing of the molecule; in this instance the orientation of two naphthyl in neighbouring molecules is nearly parallel. The structure of the diboronic acid is dominated by intra- and intermolecular hydrogen bonding.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300718
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    Temperature-dependent Ring-Opening and -Closure of a Cyclic Phosphane-BoraneDedicated to Professor Gottfried Huttner on the occasion of his 65th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 951-954 
    Details
    ISSN: 0009-2940
    Keywords: Phosphane-boranes ; Medium-sized rings ; Ring opening and closure ; Temperature-dependent NMR studies ; Phosphorus ; Boron ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A phosphane-borane (3) with the P-B bond integrated into a seven-membered ring was prepared from 4-pentenyl-diphenylphosphane (4) by hydroboration using 9-borabicyclononane (9-BBN). The product was confirmed to have a ring structure in the solid state by single crystal X-ray diffraction. The P-B distance of 2.057(2) Å is indicative of a standard donor-acceptor bond similar to the type found in homologous five- and six-membered rings. The room-temperature 31P-NMR signal of the compound in various solvents (δ ≈ - 15) is not compatible with the cyclic structure and suggests that ring opening occurs as the compound is dissolved. Variable-temperature NMR work corroborated this assumption, and the enthalpy of ring closure was determined to be ΔH = -30.5(4) kJmol-l. In CD2C12 at -90°C, δ31P is shifted to +3.5 ppm to low field, suggesting virtually complete ring closure under these conditions.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300722
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  • 78
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    The Coordination Chemistry of Fluorocarbons: Group-I and Group- II Metal Ion Complexes of Fluoro Macrocycles (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 963-968 
    Details
    ISSN: 0009-2940
    Keywords: Fluorine ; Macrocycles ; Complexes ; Sodium ; Barium ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two new fluoro macrocycles BenzoFN2O3 and F(N2O2)2C2H4 were synthesized in the reactions of 1,3-bis(bromomethyl)-2-fluorobenzene with benzo-diaza-15-crown-5 and 1,2-bis(diaza-12-crown-4)ethane, respectively, in 30% yield each. Close CF...metal ion interactions in the respective alkaline metal complexes in solution are evidenced by characteristic shifts of the 19F-NMR resonances of up to δ = 18.7 relative to the free ligand and by a decrease of the 1J(CF) coupling constant of up to 20 Hz, which is most pronounced in BenzoFN2O3 · Li+ and F(N2O2)2C2H4 · K+. In BenzoFN2O3· Li+ a1J(19F-7Li) of 15.5 Hz was observed, which is indicative very close CF...Li+ interactions in solution. In the X-ray crystal structures of BenzoFN2O3 · Na+ [CF⃛Na+ 246.8(2) pm], 26-fluoro-4,7,13,16-tetraoxa-1, 10-diazatricyclo[ 8.8.7.1 20,24 ] - hexacosa-20,22,24(26)triene · Na+ (CF⃛Na+ 267.1(2) pm) and 21 -fluoro-3,6,9,12,15,18-hexaoxabicyclo[ 18.3.1 1,20]heneicosa- l(24),20,22-triene. Ba2+ [CF⃛Ba2+ 299.0(3) pm] short CF⃛metal interactions were found. Such close CF⃛metal ion interactions do not result in a lengthening of the C-F bonds, which is not a sign of weak CF⃛metal ion interactions, since a Cambridge Structural Database search revealed that a shortening of the C-O bond length is also not observed in crown ether complexes of alkaline metals.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300725
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  • 79
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    Organophosphorus Compounds, 118Part 2: 117: Ref1. Reactions of 1-Chloro-1H-phosphirenes with Nucleophiles (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 711-723 
    Details
    ISSN: 0009-2940
    Keywords: Phosphorus heterocycles ; 1H-Phosphirenes ; Nucleophilic substitution reactions at 1H-phosphirenes ; Metal-complexation of functionalized 1H-phosphirenes ; Carbonyl complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The halogen atoms in the 1-chloro-1H-phosphirenes, 5a-c, are easily substituted on reaction with organolithium and Grignard reagents, 14a-p, with formation of the corresponding O-, N-, C-, Si-, and Ge-substituted 1H-phosphirenes, 15a-t. C1/H exchange reactions also occur on reaction with lithium metal hydrides (5a → 17). Furthermore, substitution reactions are also realized with the alkali metal borates, 18a-g (→19a-g); the same is true for reactions with trimethylsilyl cyanide and azide (→22a-d). Some of the substitution products have been characterized in the form of their metal complexes, 16, 23, 24, and 25.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/cber.19971300607
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  • 80
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    Synthesis of Germatranyl Derivatives of Esters of Carboxylic Acids via Organometallic (Si, Ge, Sn) Reagents (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 739-746 
    Details
    ISSN: 0009-2940
    Keywords: Germatranes ; Organotrihalogenogermanes ; Organometallic (Si, Ge, Sn) reagents ; Transmetallation ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Trialkylstannyl esters of tris(2-hydroxyalkyl)amines, N(CH2CHROSnAlk3)3 (9-11 (R = H, Me; Alk = Et, Bu), react with X3GeC(R1)(R2)COOR3 (12-17) (X = Cl or Br; R1, R2=H, Me, Ph, SiMe3, COOEt; R3=Me, Et) to give esters of α-germatranylcarboxylic acids, N(CH2CHRO)3GeC(R1)(R2)-COOR3 (1-8), in high yields. The synthesis of esters 12-17 is reported. Esters of α-germatranyldiphenylacetic acid 24 and 25 can be obtained by treatment of diphenylketene with Et3SnOMe to give in situ Et3SnC(Ph2)COOMe (23), followed by reaction with GeCl4 to give in situ Cl3GeC(Ph2)COOMe (22 and further reactions with 9 or 11, respectively. Reduction of germatrane 6 with LiAlH4 in diethyl ether leads to cleavage of the germanium-carbon bond with subsequent formation of (2-hydroxyethyl)trimethylsilane. The crystal structures of 3, 6 and 7 are reported. 1-Acyloxygermatranes 26 and 27 are obtained by treatment of 1-methoxygermatrane (28) with diphenyl- and dichloroacetic acid, respectively.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300611
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  • 81
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    Base-Induced Synthesis of a Tetrastannatriazabicyclo[3.1.1]heptane from Tris)dimethylchlorostannyl)amineDedicated to Professor W. Sieber on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 765-769 
    Details
    ISSN: 0009-2940
    Keywords: Tin - Nitrogen cage compounds ; Sn—X—Sn intramolecular bridges ; Distannylamine pyridine adduct ; Tin ; Moessbauer spectroscopy ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tris(dimethylchlorostannyl)amine (2a) reacts with pyridine in a 3:4 molar ratio to produce the tin-nitrogen containing bicyclo[3.1.1]heptane (3) with elimination of the adduct Me2SnCl2·2 py. Treatment of the distannylamine 2,6-[Pr2H3N(SnMe2Cl)2 (4) with pyridine, however, leads to the formation of the 1:1 pyridine adduct 4 and this can be regarded as a model to explain the route to 3. The molecular structures of 3 and 5 were determined by multinuclear magnetic resonance spectroscopy in solution, as well as by X-ray structure analysis of their crystals. Typical structural features for both compounds are intramolecular Sn—X—Sn bridges. Support for the structures comes from MS fragmentation patterns, IR spectra, and the Mössbauer spectra.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300615
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  • 82
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    Thermal Reactions of 5-Alkylidene-4,5-dihydro-3H-1,2,4(λ3)-diazaphospholes (4-Phosphapyrazolines) - A Route to Various P—Heterocycles and to 2-PhosphabutadienesDedicated to Professor M. Hanack on the occasion of his 65th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 779-788 
    Details
    ISSN: 0009-2940
    Keywords: 1,2,4-Diazaphospholes ; Phosphiranes, alkylidene- ; 2-Phosphabutadienes ; Phosphorus heterocycles ; pyrazolines, thermolysis ; Rearrangements ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 5-alkylidene-4,5-dihydro-3H-1,2,4(λ3)-diazaphospholes (4-phosphapyrazolines) are thermally much more stable than related compounds without the exocyclic double bond. Thermolysis reactions typically occur in the range 110-150°C in toluene solution, and different, mostly competing, reaction pathways are observed. Thermal extrusion of nitrogen from 8a-g gives rise to β-phosphanaylsiloxyalkenes 10, benzo[c]-phosphole derivatives 11, 14 and 115, (β-siloxyalkylidene)-Phosphiranes 12, and dihydro-1,3-oxaphospholes 13. The thermolysis of 5-alkylidene-4,5-dihydro-4-trimethylsilyl-3-trimethylsilyloxy-3H-1,2,4-dizaphospholes 17 afforded three products, including the highly substituted and stable 2-phosphabutadienes 18 formed by nitrogen extrusion and rearrangement. Finally, the 4-chloro-3-trimethylsilyloxy-substituted heterocycle 21 was transformed at 170°C into 4H-1,2,4-diazaphosphole 23. The structures of 13c and 18a were determined by single-crystal X-ray diffraction.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300617
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  • 83
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    Reaction of 1,3-Dialkyl-4,5-dimethylimidazol-2-ylidenes with 2-Bromo-2,3-dihydro-1H-1,3,2-diazaboroles (Alkyl=iPr and tBu)Dedicated to professor Adolf Zschunke on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 705-710 
    Details
    ISSN: 0009-2940
    Keywords: Boron ; Diazaboroles ; Carbenes ; Heterocycles ; Imidazoles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 2-Bromo-2,3-dihydro-1H-1,3,2-diazaboroles (3a-c) were synthesized by cyclocondensation of dilithiated 1,4-diazabutadienes (5a-c) with boron tribromide in hexane. 3a was also obtained by sodium amalgam reduction was conducted in ether solvents, diboroxane (2) resulted as the main product. Compound 3a and 1,3-dialkyl-4,5-dimethylimidazol2-ylidenes (6a, b) underwent halide displacement to afford the borolylimidazolium salts 7a, b. Compounds 2, 3a-c, and 7a, b were characterized by elemental analyses and spectroscopic methods (1H, 11B, 13C NMR; Ir; MS). The molecular structures of 2 and 7a were established by single-crystal X-ray diffraction analyses.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300606
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  • 84
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    Well-Defined Metallodendrimers by Site-Specific Complexation (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 725-728 
    Details
    ISSN: 0009-2940
    Keywords: Dendrimers ; Metal complexes ; Nanostructures ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Strong multiple complexation of transition metal ions, Cu(II), Zn(II) and Ni(II) with different generations of well-defined poly(propylene imine) dendrimers as multi(tridentate) ligands has been used to construct nanoscopic assemblies of defined structure and size incorporating a distinct number of metal ions from 2 up to 32.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300608
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  • 85
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    Compounds of Germanium and Tin, 2lPart 20: Ref.[1]. A Tetraaryldigermene with a Short Germanium-Germanium Double Bond and a Nearly Planar Environment of Both Germanium AtomsDedicated to Professor Hans Bürger on the occasion of his 6oth birthday (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 735-738 
    Details
    ISSN: 0009-2940
    Keywords: Germanium ; Digermenes ; Tin ; Germylenes ; Stannylenes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of GeCl2 · dioxane with the Grignard reagent RMgBr (R=2-tBu-4,5,6-Me3C6H) furnishes the tetraaryldigermene R2Ge=GeR2 (8). X-ray structure-analysis of 8 reveals a short Ge=Ge double bond, a nearly planar environment of both germanium atoms and extremely widened C—Ge—C angles of 128°. In solution, 8 dissociates into two germylene molecules R2Ge, which can be trapped with oxygen or by [4+1] cycloaddition reactions with 1,4-dihetero-1,3-dienes. A similar cycloadduct of a stannylene wa obtained by thermolysis of (R′2Sn)3 (R′=2,4,6-iPr3C6H2), in the presence of a 1,4-diazabutadiene and characterized by an X-ray structure-analysis.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300610
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  • 86
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    Synthesis and Crystal Structure of tert-Butylamino)di-tert-butyl)siliceniotrichloroaluminate, (Me3C)2Si=NCMe3·AlCl3, and Dimethylazomethine-Aluminium Trichloride, Me2C=NH·AlCl3Dedicated to Prof. A. Meller on the occasion of his 65th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 753-755 
    Details
    ISSN: 0009-2940
    Keywords: Silicenium ion ; Iminosilane ; Aluminate ; Silicon ; Aluminium ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Lithiated text-butylaminolfluorosilanes react with aluminum trichloride in ether, eliminating LiF to give AlCl3 adducts of iminosilanes  -  aminosiliceniotrichloroaluminates {R2Si-NCMe3·AlCl3}, which thermally form the dimethylazomethine- aluminium trichloride, Me2C=NH·AlCl3.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300613
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  • 87
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    Sulfur Compounds, 199Part 198: R. Steudel, Y Drozdova, K. Miaskiewicz, R. H. Hertwig, W. Koch, J Am. Chem. Soc. 1997, 119, 1990.. Novel Titanocene Thiolato Complexes and Their Application in Preparing New Sulfur-Containing Heterocycles (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 757-764 
    Details
    ISSN: 0009-2940
    Keywords: Titanocene complexes ; S ligands ; Organic polysulfanes ; Ligand transfer reactions ; Sulfur heterocycles ; Chalcogens ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Treatment of Cp2Ti(CO)2 (3) with the di- and polysulfanes 1,2,4-(CH2)2S3, C4S6 (9), C,7H10S3 (11), 1,2,4,6-(CH2)3S4 (16), C6H10S6(19), and S6 affords the titanocene chelate complexes Cp2TiS3(CH2)2 (8), (Cp2Ti)2C4S6 (10), Cp2TiS3C7H10 (13), Cp2TiS2C7H10 (14), Cp2TiS4(CH2)3 (17), Cp,2TiS6C6H6H10 (20), and Cp2TiS8 (23). 14 is also obtained from Cp2TiCl2 (1) and the geminal dithiol of norbornene. The analogous reaction with the dithiol of dicyclopentadiene yields Cp2TiS2C10H12 (15). In ligand transfer reactions, 8 reacts with SCl2 to give 1,2,3,5-tetrathiane (25), 10 provides 9 on reaction with Cl2, 13 when treated with S2Cl2 affords C7H10S5 (12), 15 reacts with S2Cl2Cl2 to give C10H12S4. 17 and SCl2 yield 1,2,3,5,7-pentathiepane (18), 20 is converted to C6H10S7 (22) on reaction with SCl2, and 23 yields S10 and 1,2,-C6H4(SCl)2, respectively. With phosgene, thiophosgene, and thionyl chloride, compound 15 yields the corresponding dithiocarbonate 26, the trithiocarbonate 27 and the trisulfane 2-oxide 28. The structure of 27 was determined by X-ray crystallography.
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    URL: http://dx.doi.org/10.1002/cber.19971300614
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  • 88
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    Synthesis of a Bisdienophilic Phthalocyanine and of Precursors for Repetitive Diels-Alder Reactions Based on Hemiporphyrazines and Phthalocyanines (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 801-806 
    Details
    ISSN: 0009-2940
    Keywords: Unsymmetrical phthalocyanines ; Hemiporphyrazines ; Macrocyclic bisdienes and bisdienophiles ; Diels-Alder reactions ; Ladder polymers ; Cycloaddition ; Macrocycles ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The specific synthesis of a metal-free bisdienophilic phthalocyanine 193, suitable for repetitive Diels-Alder reactions, is reported. This was achieved by condensation of 191,3,3-trichloro-6/7-nitroioindolenine (191) and 4,9-dibutoxy-2,3,5,8-tetrahydro-1,3-diimino-1H-5,8-epoxybenz[f]isoindoline (2). The ability of 3 to undergo Diels-Alder reactions was tested by reaction with an excess of 1,2,3,4-tetraphenylcyclopentadienone (5). Experimental data of the hemiporphyrazines 9, 10, and 11, which can be used as precursors for the synthesis of ladder polymers, are also given in the Experimental Section.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300620
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  • 89
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    Pseudoelement Compounds, XPart IX: Ref. Synthesis and Crystal Structure of New Complexes of the Type trans-[Pt(H)X(PPh3)2 with Cyanamide and Cyanomethanide LigandsDedicated to Professor S. Engels on the occasion of his 65th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1007-1012 
    Details
    ISSN: 0009-2940
    Keywords: Platinum ; Nitrocyanamide ; Nitrosodicyanomethanide ; 1,1,3, 3-Tetracyano-2-azapropenide ; 1,1,2,3,3-Pentacyanopropenide ; Hydrido complexes ; Coordination modes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The new coordination compounds trans-[Pt(H)X(PPh3)2] with NCN- and C(CN)2-functionalized anions (X- = [N(O)C(CN)2]-, [NO2NCN]-, [N{C(CN)2}2]-, [NCC{C-(CN)2}2]-, have been characterized by 1H-, 31P-, 13C-NMR, and IR spectroscopy and elemental analyses the crystal structures of trans-[Pt(H)N(O)C(CN)2(PPh3)2], trans- [Pt(H)N{C(CN)2}2(PPh3)2], and trans-[Pt(H)NCC{C(CN)2}2-(PPh3)2) have been determined by X-ray diffraction. Remarkably, [N(O)C(CN)2]- is coordinated through the central nitrogen atom, while [N{C(CN)2}2]- and [NCC(C(CN)2]2]- are bonded through terminal nitrogen atoms of a C(CN)2 unit.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/cber.19971300730
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  • 90
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    New Coupling Reactions and Phosphorylations Using Organozinc Reagents (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1021-1027 
    Details
    ISSN: 0009-2940
    Keywords: Zinc ; Chirality ; Cross-coupling ; Phosphorylations ; Catalysis ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This Microreview on the chemistry of organozinc reagents starts by briefly showing the methods of preparation of organozinc compounds and then discusses the considerable synthetic utility of zinc organometallics for the formation of new carbon-carbon bonds in the presence of transition-metal catalysts. Finally, the use of organozinc chemistry for the preparation of polyfunctional and chiral phosphanes is described.
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    URL: http://dx.doi.org/10.1002/cber.19971300802
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  • 91
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    Synthesis and Structures of Bis(tetramethylipiperidino)aluminum Halides-X-ray Crystal Structures of tmp2AlX (X = Cl, Br, I) and [tmp2A1(μ-F)l2 (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1047-1052 
    Details
    ISSN: 0009-2940
    Keywords: Bis(tetramethylipiperidino)aluminum halides ; Alkoxy((tetramethylpiperidino)aluminum halides ; 27Al-NMR spectra ; Aluminum ; Amides ; Synthetic methods ; Bridging ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-Lithio-2,2,6,6-tetramethylpiperidine [Li(tmp)] reacts with AlX3 (X = Cl, Br) in diethyl ether/ n-hexane solution to generate the products of substitution and ether cleavage, [tmpAl(X)(μ-OEt)], (la, X = Cl; 1b, X = Br). However, when the reaction is allowed to proceed in n-hexane alone, an almost quantitative yield of compounds tmp2AlX (2a, X = Cl; 2b, X = Br; 2c, X = I) is obtained. According to 27AI-NMR spectroscopy, mass spectroscopy, cryoscopy, and X-ray crystal structure determinations, these compounds are monomeric in the solid state, in solution, and in the gas phase. 2b reacts with AgBF4 yielding the fluoride-bridged dimer (tmp2AlF), 2d, as shown by X-ray crystal structure determination.
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    URL: http://dx.doi.org/10.1002/cber.19971300805
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  • 92
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    Synthesis, Structure, and Dynamic Behavior of (μ-Aldimido)(μ-η1: η2-alkyne)- biszirconocene Cation Complexes That Contain Planar-Tetracoordinate Carbon (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1069-1077 
    Details
    ISSN: 0009-2940
    Keywords: Planar-tetracoordinate carbon ; Dynamic organometallic systems, μ-alkyne complexes ; π-Agostic systems ; Zirconium ; Metallocenes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The benzonitrile hydrozirconation product Cp2ZrCl(N—CHPh) 8 was treated with propynyl lithium to yield the (propynyl)(benzaldimido)ZrCp; complex 9. Subsequent treatment with trityl tetraphenylborate generated [Cp2Zr(C—C—CH3)-BPh-4] that instantaneously added to 9 to eventually form the (μ-aldimido)(μ-η1:η2-hexadiyne)ZrCp2 cation 11. The X-ray crystal structure analysis showed that 11 contains a planar-tetracoordinate carbon atom that is stabilized by forming a three-center-two-electron bond with the two adjacent metal atoms. Similarly, complex 9 reacted with [Cp2Zr(CH3)+CH3B(C6F5)3 1 to yield the planar-tetracoordinate carbon containing (μ-aldimido)(μ-η1:η2-2-butyne) Cp; cation 12. Both complexes 11 and 12 exhibit dynamic NMR spectra due to their rapid reorganization of the dimetallabicyclic frameworks (ΔG* = 10 kcal mol-1) in addition to an anchimerically assisted C—N bond rotation (ΔG* =15 kcal mol-1).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300808
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    Isolation and Characterization of a Porphinatomanganese(IV) Complex from the Reaction of Dichloro Monoxide with 5,10,15,20-Tetrakis-(2,6-dichloropheny)porphinatomanganese(III) Chloride [Mn(EDCPP)CI] (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1099-1103 
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    ISSN: 0009-2940
    Keywords: Porphyrinatomanganese(IV) ; Monooxygenase model ; Dichloro monoxide ; Catalytic alkene epoxidation ; Catalytic alkane oxygenation ; Catalytic alkane chlorination ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The isolation at -78°C and characterization of the novel crystalline reactive porphinatomanganese(IV) complex Mn-(TDCPP)(OCl)2 (5) is described. 5 is compared with the porphinatomanganese(IV) complexes Mn(TDCPP)(C6H5IOCl)2 (2), Mn(TDCPP)(C6F510C1)CI (3) and Mn(TDCPP)(OCH3)2, (4). The stoichiometric reaction of 5 with triphenylphosphane yields 2.5 equivalents of triphenylphosphane oxide and 1.0 equivalent of Mn(TDCPP)Cl (1). Complex 5 epoxidizes stilbene, and oxygenates and chlorinates cyclohexane.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300811
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  • 94
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    Synthesis and Structure of Allenyl-Substituted η6-Benzene(tricarbonyl)-chromium Complexes (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1135-1139 
    Details
    ISSN: 0009-2940
    Keywords: Arene complexes ; Chromium ; Allenes ; Rearrangements ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Cr(CO)3-complexed η6-phenylpropargylic alcohols 3 react in a displacement rearrangement with thionyl chloride or chlorodiphenylphosphane to give the chloro- or phosphoryl allenyl substituted η6-phenyl complexes 4 and 6, respectively. In the X-ray crystal structure of the novel organometallic allenic derivatives 4b and 6b the vicinal chloro or phosphoryl substituent and the benzene(tricarbonyl)chromium fragment are arranged coplanarily. Palladium/copper-catalyzed couplings of the chloroallene 4b with terminal alkynes disclose a facile access to ynallene derivatives 8, novel carbon-rich organometallic π-systems.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300816
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  • 95
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    Raman and Infrared Spectra and Quantum Chemical Calculations for Trichlorophosphoranylidenesulfamoyl Chloride, CISO2N=PCI3 (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1141-1145 
    Details
    ISSN: 0009-2940
    Keywords: Trichlorophosphoranylidenesulfamoyl chloride ; Vibrational spectroscopy ; Conformational properties ; Quantum chemical calculations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Raman (3500-50 cm-l) and infrared (4000-400 cm-l) spectra of the title compound, ClSO2N=PCl3, were recorded for the solid and liquid phase. Additionally, the Raman spectrum of the compound dissolved in CCl4 was obtained and qualitative depolarization values were determined. The spectra of the liquid and solid phase were interpreted in terms of the existence of only one conformation possessing C1 symmetry, as predicted by quantum chemical calculations. A complete vibrational assignment is proposed based on the relative intensities, on group frequencies along with support from the normal coordinate analysis. The experimental fundamental vibrational modes are compared to those obtained from theoretical approaches employing the ab initio MP2/6-31G* method and a density functional approximation (B3PW91/6-31G*).
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300817
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  • 96
    Electronic Resource
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    Ab Initio Studies on Disubstituted closo-Icosahedral Heteroboranes, X2B10H10 [X = CH, SiH, N, P, and Sb] (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1147-1150 
    Details
    ISSN: 0009-2940
    Keywords: Icosahedral heteroboranes ; Ab initio calculation ; Bonding models ; Aromaticity ; Nucleus Independent Chemical Shift [NICS] ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ab initio theoretical studies on X2B10H10 (X = CH, SiH, N, P and Sb) have been done for all the three possible isomers. Unlike lower-vertex heteroboranes, all the hetero derivatives have shown similar trends in the relative stabilities, the 1,12-isomer being more stable followed by 1,7- and 1,2-isomers, except for N and Sb. No conventional 1,2-isomer for N could be found. Instead, a new nido isomer which is 18.1 kcal/mol higher in energy than the most stable isomer has been located. Any hetero group substitution to icosahedral R12H122- is found to be thermodynamically destabilizing. However, the Nucleus Independent Chemical Shift criterion shows that all compounds, except for 8, have similar aromaticity.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300818
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  • 97
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    The Molecular Structures of Triaminosilanes (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1159-1166 
    Details
    ISSN: 0009-2940
    Keywords: Aminosilantes ; Structure elucidation ; Molecular conformations ; Configuration determination ; Nitrogen Planarity/Silanes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structural chemistry of a series of triaminosilanes XSi(NR2)3 has been investigated in order to determine the ground-state configuration and conformation of these molecules. Theoretical studies and analogy with the isoelectronic XP(NR2)3 (X = CH2, O, Se, NSiMe3 etc.) and P(NR2)3 molecules suggest structures of Cs or C3 symmetry, with small energy differences between them. The molecular structure of HSi(NMe2)3 (1) has been determined by a single-crystal X-ray diffraction study at low temperature. Surprisingly, the molecules have a non-standard conformation with an irregular orientation of the three NMe2 groups. The hydrido-, chloro-, methyl-, and vinyltris(morpholino)silanes XSi[N(CH2CH2)2O]3 (X = H, Cl, Me, Vi; 2-5) were prepared from the corresponding chlorosilanes and morpholine (2, 3) or lithium morpholide (4,5). Their variable-temperature NMR spectra were studied and the molecular structures determined by single crystal X-ray diffraction. Compound 2 has a molecular geometry approaching mirror symmetry with one morpholino group significantly different from the other two. This structure resembles that of isoelectronic tris(amino)phosphines. Compounds 3-5 have structures with a propeller-like arrangement of the three morpholino rings approaching C3 symmetry for this part of the molecules. The chloro compound 3 shows the shortest Si-N bond lengths (average 1.690 Å), followed by 2 (1.708Å),5 (1.709Å) and 4 (l.712Å). The configuration of all nitrogen atoms is almost planar, with sums of the angles close to 360°, and the morpholino rings adopt a chair conformation. According to the solution NMR spectra the ring inversion is slow at low temperature, but the rings rotate freely about the Si-N bonds on the NMR time scale. The molecular structures are discussed in terms of steric and electronic effects of the substituents. Other model compounds, including (Me2N)3SiC6H4-4-Br (6), MeSi[N(CH2CH2)2NMe]3 (7) and PhSi[N(CH2)4]3 (8), could not be crystallized, but were characterized by their analytical and spectroscopic data.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300820
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  • 98
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    A Monomeric Bis(arena)lead(II) Complex with a Plumbocene-like Bent Sandwich Structural Unit  -  Structure of [Pb(1,2-C6H4Me2)2(AlCl4)2Dedicated to Professor C. G. Kreiter on the occasion of his 60th birthday. (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1731-1732 
    Details
    ISSN: 0009-2940
    Keywords: Lead ; Tetrachloroaluminate ; Arenes ; o-Xylene ; Bis(arene) Complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis(o-xylene)lead(II) bis(tetrachloroaluminate), obtained from lead(II) chloride and aluminium trichloride in o-xylene, has been shown by X-ray crystallography to be a mononuclear lead complex with point group symmetry C2 The two aromatic ligands are arranged similarly to those in monomeric plumbocene. The coordination sphere is completed by two bidentate AlCl4-ions. The lead center uses about a quarter of its bonding capability for each of the four ligands
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301204
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  • 99
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    Titanium and Zirconium Complexes Containing a Novel Dianionic Trifunctional Amido Ligand (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1751-1759 
    Details
    ISSN: 0009-2940
    Keywords: Amido complexes ; Titanium ; Zirconium ; Alkylmetal compounds ; Amido complexes ; Titanium ; Zirconium ; Alkylmetal compounds ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The novel tridentate diamidoamine ligands [RC(2C5H4N)(CH2NSiMe3)2)2- (R = H, CH3) have been synthesized and coordinated to TiIV giving the pentacoordinate complexes [MX2(RC(2-C5H4N)(CH2NSiMe3)2}] (M = Ti, Zr; X = Cl, Br). The crystal structure analysis of [TiBr2{HC(2-C5H4N)(CH2)2}] (M = Ti, Zr; X = Cl, Br). The crystal structure analysis of [TiBr2{HC(2-C5H4N)(CH2NSiMe3))] (10b) confirmed the involvement of the pyridyl function in the coordination to the meta centre occupying an apical position in the trigonal bipyramidal ligand polyhedron. alkylation of [TiCl2{H3CC(2-C5H4N)(CH2NSiMe3)2)] (12a) with one or two molar equivalents of [RMgCl](R = PhCH2, Me3SiC2) yielded the mono- and dialkyl complexes [TiClR{H3CC(2-C5H4N)(CH2NSiMe3)2)] and [TiR2(H3CC(2-C5H4N)(CH2NSiMe3)2)] and [TiR2(H3CC(2-C5H4N)(CH2NSiMe3)2}] in good yields. Depending on the steric demand of the alkyl group coordination or decoordination of the pyridyl group leads to four- or five-coordinate species. A crystal structure analysis of the pentacoordinate complex [TiCl(CH2SiMe3){H3CC(2-C5H4N)(CH2NSiMe3)2}] (16) was carried out.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301208
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  • 100
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    Masthead (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997) 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301101
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