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  • 1
    Electronic Resource
    Electronic Resource
    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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  • 2
    Electronic Resource
    Electronic Resource
    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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971300607
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  • 3
    Electronic Resource
    Electronic Resource
    Derivatives of Aza-nido-tetraborane and Diaza-arachno-pentaborane from Tri-tert-butylazadiboriridine (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1-9 
    Details
    ISSN: 0009-2940
    Keywords: 1-Aza-nido-tetraboranes ; 2,5-Diaza-arachno-pentaboranes ; 2,5-Diaza-nido-hexaboranes ; Boryl[diborane(4)yl]amine ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Lewis acids RBH2 are added to the basis B-B bond of tri-tert-butylazadiboriridine, NB2tBu3 (1a), to give 5-alkyl-1,2,3-tri-tert-butyl-1-aza-nido-tetraboranes of type 3 (two endo-H atoms at B5) or type 4 (one H atom in a B2-B5 bridging position, one exo-H atom at B5), either as a mixture of 3 and 4 (3, 4b-d: R = Me, tBu, CMe2iPr) or with the isomer 4 in high excess (4e, f: R = Ph, sBu). The reaction of dialkylboranes R2BH with 1a yields 5,5-dialkyl-1,2,3-tri-tert-butyl-1-aza-nido-tetraboranes of type 4 (one H atom in a B2-B5 bridging position; 4g, h: R2 = Et2, cycloocta-1,5-diyl). In boiling THF, trialkylboranes BR3 transform 1a into NB2tBu2R which, expectedly, dimerizes spontaneously to give a dialkyltetra-tert-butyl-2,5-diaza-nido-hexaborane of type 2 (2a, b: R = Me, Et). The products of the addition of aminoboranes H2B=NRR' to 1a are identified as alkyl derivatives of 2,5-diaza-arachno-pentaborane, N2B3tH2tBu3RR' (5a-d, R/R' = H/Pr, H/tBu, Me/Me, Et/Et). The aminoborane H2B = NiPr2 with a sterically more demanding amino group hydroborates the B-B bond of 1a to give the acyclic product iPr2N=BH-B(tBu)-N(tBu)=B(tBu)H (6). In contrast to the B atoms, the N atoms in the electron-deficient cluster skeletons of 2-5 need not take part in (3c,2e) bonds of the s̰ type. The molecular structures of 4c, 5d, and 6 are confirmed by X-ray structural analyses.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280102
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  • 4
    Electronic Resource
    Electronic Resource
    Organometallic Aqua Complexes, IIIPart II: Ref.[1].. Olefin Aqua Complexes of Rhodium(I) (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 911-917 
    Details
    ISSN: 0009-2940
    Keywords: Rh coordination complex ; Organometallic aqua ions ; Olefin complex ; Olefin exchange ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dehalogenation of halide precursors [(olefin)RhCl]2 [olefin = ethylene, 1,5-cyclooctadiene (COD], norbornadiene (NBD), 2,3-dimethylbutadiene (DMB)] in water gave the respective cis-diolefin aqua ions, characterized by NMR spectroscopy in solution. Attempted isolation of the tosylate salt [(COD)Rh-(H2O)2]OTs yielded crystals of (COD)Rh(H2O)(η1-OTs) characterized by X-ray structural analysis. [(NBD]Rh(H2O)2]SbF6 in the presence of adventitious toluene decomposed into [(NBD])Rh(η6-toluene)]SbF6 and [(NBD]2Rh]SbF6, both complexes were isolated and structurally characterized. Ethylene exchange in [(C2H4)2Rh(H2O)2]+ is fast with k2 of the order of 104-105 s-1 · M-1. The rate constant for water exchange in [CODRh(H2O)2]+ is estimated as 104 s-1 (ΔDLG≠173 ≍ 25 kJ/mol) at 173 K.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951280910
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  • 5
    Electronic Resource
    Electronic Resource
    Oligonuclear Organometallic Complexes with Boron-Nitrogen Bridges (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1163-1169 
    Details
    ISSN: 0009-2940
    Keywords: Ferrocenylboranes ; Chromium, (aniline)tricarbonyl- ; Polynuclear complexes ; Boron-nitrogen bridges ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The facile formation of boron-nitrogen bridges allows the one-step assembly of oligonuclear organometallic complexes. By the reaction of 1-(dibromoboryl)ferrocene (1a) and 1,1′-bis(dibromoboryl)ferrocene (1b) with 1-[(dimethylamino)methyl]ferrocene (2) and (η6-aniline)tricarbonylchromium derivatives (3, 4) dinuclear to pentanuclear units (5-10) were obtained. The homodimetallic compound FcBBr2-NMe2CH2Fc (5, Fc: ferrocene) closely resembles a propylene-bridged complex. Its dative B-N link is stable at temperatures as high as 100°C. Each of the heterooligonuclear aggregates 7-10 is tied together by covalent B-N bonds, which are isoelectronic with ethylene bridges. In FcB(Br)-N(Me)Bct [7, Bct: (η6-C6H5)Cr(CO3)] and 1,1′-Fc[B(Br)-N(Me)Bct]2 (9) B-N π bonding dominates over the N-Bct π interaction as indicated by spectroscopical data and an X-ray analysis of 9. The N-lithiated compounds BctNRLi (4a, b; R = H, Me) possess a remarkably increased N-Bct π donation compared to the protonated parent compounds, which results in a further perturbation of the local C3v symmetry of the (C6H5)Cr(CO3) framework.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951281205
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  • 6
    Electronic Resource
    Electronic Resource
    Novel Ferrocene-Based Mono- and Bifunctional Tri-1-pyrazolylborate Ligands (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 603-606 
    Details
    ISSN: 0009-2940
    Keywords: Ferrocenylboranes ; Tri-l-pyrazolylborate ligands ; Oligometallic complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of (dibromoboryl)ferrocene (1a) with pyrazole/NEt3 gave the ferrocenyltri-1-pyrazolylborate ligand 2. Its thallium(I) derivative 2-Tl provides the first example of a polymeric structure with bridging tri-1-pyrazolylborate units in the solid state. The trinuclear iron complex 2-Fe, which is related to 1,1′-terferrocene, was obtained by reaction of 2 with FeCl2. The bis(polydentate) ligand 1,1′-ferrocenediyl-bis(tri-1-pyrazolylborate) (3-Li) was prepared from 1,1′-bis-[bis(dimethylamino)boryl]ferrocene (1c) and a mixture of lithium pyrazolide/pyrazole in refluxing toluene/THF. 3-Li reacts with TlNO3 to give the thallium(I) complex 3-Tl.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961290603
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  • 7
    Electronic Resource
    Electronic Resource
    Dithio and Thiono Esters, 62Part 61: K. Hartke, S. Barrmeyer, J. Prakt. Chem., in press.. Reactions of Alkanedithioic Acid Dianions with Iodine, Sulfur, and Tin CompoundsDedicated to Prof. Dr. Kurt Dehnicke on the occasion of his 65th birthday. (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 663-669 
    Details
    ISSN: 0009-2940
    Keywords: Alkanedithioic acid ; Dithiocarboxylic acid ; 1,2-Dithiine ; 1,2,4-Trithiolane ; 1,2,3,4-Tetrathiane ; 1,3,2-Dithiastannetane ; Thioacyltin sulfide ; Bis(thioacyl)tin sulfide ; 1,2,3,4,5,6-Hexathiepane ; 1,2,3,5,6,7-Hexathiocane ; 1,2,3,5,6-Pentathiepane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The monoanion of the alkanedithioic acid 1a is oxidized with hypervalent iodine compounds to form the 1,2-dithiine 6, the monoanion of 1b yields the 1,2,4-trithiolane 7 and the dianions 2b, c furnish the 1,2,4,5-tetrathianes 3b, c. With diphenyltin or dimethyltin dichlorides 8 the monoanions of 1b, c afford the monothioacyl or bisthioacyl organotin sulfides 10a-c or 11a, b respectively. When treated with lithium hexamethyldisilazane, 10b undergoes an intramolecular cyclization to the 1,3,2-dithiastannetane 9b; 10a is deprotonated by triethylamine to the 1,3,5-trithia-2-stanninane 13. The dianion 2c reacts with diphenyltin dichloride 8 to yield the 1,3,2-dithiastannetane 9d, with dimethyltin dichloride the 1,2,4-trithiolane 16 is formed. 9d is cleaved by thionyl chloride, sulfur dichloride, and disulfur dichloride to give a complex mixture of the 1,2,4,5-tetrathiane 3c and the cyclic polysulfides 1,2,3,4,5,6-hexathiepane 18, 1,2,3,5,6,7-hexathiocane 19 and the 1,2,3,5,6-pentathiepane 20 in varying amounts. Reaction of the dianion 2b with thionyl chloride leads to the formation of the 1,2,4,5-tetrathiane 3b as main product; byproducts are cyclic polysulfides, the 1,2,3,5,6-pentathiepane 21 and the 1,2,3,4,5,6-hexathiepane 22.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961290612
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  • 8
    Electronic Resource
    Electronic Resource
    Diboran(4)yl Groups as Ligands to Transition Metals (1996)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 129 (1996), S. 1099-1101 
    Details
    ISSN: 0009-2940
    Keywords: Diboranes ; Transition-metal boryl complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of Na[(Cp)Fe(CO)2] and Na[(Cp)W(CO)3] with B2(NMe2)2Cl2 yields the first transition metal-substituted diboranes [Cl(Me2N)B-B(NMe2)M(Cp)(CO)n] [M(Cp)(CO)n = Fe(Cp)(CO)2, W(Cp)(CO)3] (1a, b). The compounds were characterized in solution by NMR methods and in the crystal by X-ray structural determination.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19961290919
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  • 9
    Electronic Resource
    Electronic Resource
    Polare Iminoborane: Reaktionen des (tert-Butylimino)(pentafluorphenyl)borans (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1037-1043 
    Details
    ISSN: 0009-2940
    Keywords: Iminoborane ; Triazadiboracyclohexane ; Borazine ; Diazadiboracyclobutane ; Azaboracyclobutane ; Diazadiboracyclopentane ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polar Iminoboranes: Reactions of (tert-Butylimino)(pentafluorophenyl)boraneThe reactions of the iminoborane C6F5-B≡N-tBu (1) with nitriles and isonitriles are studied. Nitriles RCN give cycloadducts either of the triazadiboracyclohexane type (3a; R = iPr) or of the tetrazatriborabicyclo[4.2.0]octane type [4b-d; R = Ph, p-C6H4Me, p-C6H4(CF3)] or of the (iminomethyl)borazine type (5e, f; R = Me, Et). Isonitriles RNC yield mainly adducts of RNC to a cycloaddition product of the diazadiboracyclopentane type (6a, b; R = 2,6-C6H3Me2, tBu); the adduct of RNC to a diazadiboracyclobutane may be a side-product (7b; R = tBu). The iminoborane Me3Si(tBu)N-B=NtBu reacts with two molecules of (2,6-C6H3Me2)NC to give the corresponding azaboracyclobutane 8. The iminoborane tBu-B≡N-C6F5 (1′), formed by gas-phase elimination of ClSiMe3 from Cl(tBu)B = N(C6F5)SiMe3 (9), cyclodimerizes more readily than the isomeric borane 1. The cyclodimer 2′ gives 1:1-addition reactions with tBuNC, PMe3, and MeNC, respectively; the added components fluctuate in solutions of the products 7b'-d'. A similar fluctuation is observed with the 1:1 adduct 7c from PMe3 and the cyclodimer 2 of the iminoborane 1. The products 3a, 5e, 6a, 8 crystallize in the space groups P21/c, P21/n, Pbca, and P21/c, respectively.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951281012
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  • 10
    Electronic Resource
    Electronic Resource
    A Novel Approach to Ferrocenes with Planar Chirality (1995)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 128 (1995), S. 1157-1161 
    Details
    ISSN: 0009-2940
    Keywords: Ferrocenes, planar chiral ; Deprotonation, diastereoselective ; Palladium complexes ; Chelating P,N-ligands ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 2-metalation of enantiomerically pure (S)-(2-methoxy-methylpyrrolidin-1-yl)ferrocene FcSMP (1) with BuLi proceeds with high diastereoselectivity (up to 98% de) to yield the Ph2P-substituted ferrocene (S,Sp)-2a after quenching with Ph2PCl. The SMP moiety was removed by heating of 2a at reflux in acetic anhydride to give planar chiral (Sp)-2-diphenylphosphanylferrocenylmethyl acetate (5). The diastereoisomer (S,Rp)-2b was synthesized from 1 by intermediately blocking the primary metalation site with a Me3Si group which can be removed afterwards by treatment with KOtBu in DMSO. Compound 2a was treated with [(C3H5)PdCl]2 to give the complex [(C3H5)Pd·2a]PF6 (7·PF6). The structure of 7·PF6 was determined by a single-crystal X-ray diffraction study and showed 2a to act as a bidentate P,N-chelate ligand.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19951281204
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