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  • 1
    Electronic Resource
    Electronic Resource
    Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, LXXX. Insertions- und Additions-Reaktionen an Diphosphamanganacyclopropanen mit aktivierten Alkinen (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 23-29 
    Details
    ISSN: 0009-2940
    Keywords: Diphosphamanganacyclopropanes ; Alkyne insertion ; Alkyne addition ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metal-;Containing Heterocycles: Preparation, Properties, Reactions, LXXX.  -  Insertion and Addition Reactions on Diphosphamanganacyclopropanes with Activated AlkynesThe thermally and kinetically stable diphosphamanganabicyclooctadienones 3a  -  e [R2 = tBu: R1 = iPr (a), nPr (b), Ph (c); R2 = Cy: R1 = nPr (d), Ph (e)] are obtained by the reaction of the alkyne (CCO2Me)2 with the diphosphamanganacyclopropanes (OC)4Mn-PR12=PR2 (2a  -  e). Depending on steric factors the formation of 3a  -  e occurs in two different ways. In a first step the alkyne is inserted into the P  -  P bond of 2a  -  e to give the kinetically labile five-membered rings 1a  -  e. Subsequently another alkyne is added to the PR2 and a CO group of 1a  -  e to give 3a  -  e. In an alternative way the alkyne is added first to the PR2 and a CO group of 2a with formation of the diphosphamanganabicyclohexenone 4a. Insertion of a second alkyne into the P  -  P bond of 4a affords the bicyclooctadienone 3a. Compound 2a, 3c, and 4a have been characterized by X-ray structural analyses.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19931260105
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  • 2
    Electronic Resource
    Electronic Resource
    Synthese und Eigenschaften gemischtsubstituierter (Chloracetyl)-organylphenylphosphane (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 645-658 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Properties of Mixed Substituted (Chloroacetyl)organylphenylphosphanesThe mono-, di- and trichloroacetylorganylphenylphosphanes X1X2CClC(O)PPhR (3av - cz) are obtained by reaction of Me3SiPPhR (2v - z) [R = Me (v), Et (w), iPr (x), nPr (y), Benzyl (z)] with the acid chlorides X1X2CClC(O)Cl (1a - c). Increasing content of chlorine results in a shift of the =O band and the 31P signal to higher wavelengths and fields, respectively, in the IR and 31P{1H} NMR spectra of 3av - cz. Due to the centre of chirality at the phosphorus atom in the 1H NMR spectra one observes diastereotopic protons in the chloroacetyl moiety of 3av - az and of the P-adjacent CH2 protons of 3aw - cw and 3ay - cy. The magnetic inequivalence of both methyl substituents in the isopropyl groups of 3ax - cx is observable also in the 13C{1H} and 1H NMR spectra. Because of steric reasons the free rotation about the P-isopropyl axis is hindered up to 355 K. From the coalescence temperature the free activation energy ΔG≠ is calculated to give 74.7 kJ/mole. The degradation of the thermolabile compounds 3av - cz results in the formation of the chlorophosphanes 5v - z. Individual investigations on 3bv, 3bw and 3by indicate the formation of mono- and dichloroacetyl chloride. The appearance of ClCH2C(O)Cl proceeds via the chloroketene 4b.
    Notes: Durch Umsetzung von Me3SiPPhR (2v - z) [R = Me (v), Et (w), iPr (x), nPr (y), Benzyl (z)] mit den Säurechloriden X1X2CClC(O)Cl (1a - c) erhält man die Mono-, Di- und Trichloracetylorganylphenylphosphane X1X2CClC(O)PPhR (3av - cz). Zunehmender Chlorgehalt bewirkt in den IR- und 31P{1H}-NMR-Spektren von 3av - cz eine Verschiebung der =O-Bande und des 31P-Signals nach höheren Wellenzahlen bzw. höherem Feld. Wegen des Chiralitätszentrums am Phosphor beobachtet man in den 1H-NMR-Spektren diastereotope Protonen im Chloracetylrest von 3av - az und der P-benachbarten CH2-Protonen von 3aw - cw und 3ay - cy. Die magnetische Inäquivalenz der beiden Methylsubstituenten in den Isopropylgruppen von 3ax - cx macht sich auch in den 13C{1H}- und 1H-NMR-Spektren bemerkbar. Bis 355 K ist die freie Drehbarkeit um die P-Isopropyl-Achse aus sterischen Gründen gehindert. Aus der Koaleszenztemperatur von 3ax berechnet sich die freie Aktivierungsenthalpie ΔG≠ zu 74.7 kJ/mol. Beim Zerfall der thermolabilen Verbindungen 3av - cz entstehen die Chlorphosphane 5v - z. Spezielle Untersuchungen an 3bv, 3bw und 3by zeigen die Bildung von Mono- und Dichloracetylchlorid. Das Auftreten von ClCH2C(O)Cl verläuft über das Chlorketen 4b.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190224
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  • 3
    Electronic Resource
    Electronic Resource
    Synthese, Kristallstruktur und fluktuierendes Verhalten von cis-Cl2Ru(CO)(P∽O)(P^O) mit cis-ständigen (Ether-Phosphan)-LigandenHerrn Professor Wolfgang Beck zum 60. Geburtstag gewidmet. (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 1363-1367 
    Details
    ISSN: 0009-2940
    Keywords: Ruthenium(II) complexes ; Ether phosphanes ; Fluxional behavior ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis, Crystal Structure, and Fluxional Behavior of cis-Cl2Ru(CO)(P∽O)(P^O) with cis-Positioned (Ether-Phosphane) LigandsReaction of the ether-phosphane ligands 2a-c with Cl2Ru-(PPh3)3 (1) results in the formation of the bis(chelate) complexes trans-Cl2Ru(P^O)2 (3a-c) (P∽O = η1-P-coordinated; Pb̂O = η2-O,P-coordinated). With CO both Ru-O bonds are cleaved to give all-trans-Cl2Ru(CO)2(P∽O)2 (4a-c). The mono(chelate) complexes 5a-c are obtained from stoichiometric amounts of 3a-c and 4a-c. Upon heating the kinetically controlled products 5a-c are transformed into the thermodynamically more stable isomers cis-Cl2Ru(CO)(P∽O)(P^O) (6a-c). Both 5a-c and 6a-c show fluxional behavior. The higher coalescence temperatures and estimated ΔG≠ values of 6a-c (75, 67, and 70°C, respectively) compared to 5a-c (55, 0, and -10°C, respectively) indicate different exchange mechanisms for 5 and 6. According to an X-ray structure analysis, 6b crystallizes in the monoclinic space group P21/c with Z = 4. The action of CO on 6a-c affords the cis,cis,trans complexes 7a-c.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19921250609
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  • 4
    Electronic Resource
    Electronic Resource
    Fluktuierendes Verhalten von kationischen cis1-Bis(ether-phosphan)1-palladium(II)1-Komplexen. - 31P-DNMR-spektroskopische Untersuchungen, Linienformanalyse und Bestimmung der thermodynamischen AustauschparameterHerrn Professor Heinrich Nöth zum 65. Geburtstag gewidmet. (1993)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 126 (1993), S. 1317-1324 
    Details
    ISSN: 0009-2940
    Keywords: Palladium complexes ; Ether-phosphanes ; NMR, 31P, dynamic, line-shape analysis ; Fluxional behavior ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fluxional Behavior of Cationic cis Bis(ether-phosphane)palladium(II) Complexes. - 31P-DNMR Spectroscopic Investigations, Line-Shape Analysis, and Determination of Rearrangement BarriersHerrn Professor Heinrich Nöth zum 65. Geburtstag gewidmet.Reaction of X2Pd(P∼O)2 (X=Cl: 1a - g, k - n, p; X=Br: 1′; X=I: k″, l″, o″) with stoichiometric amounts of AgClO4 results in the formation of the monochelate complexes cis-[ClPd(P∼O)(P∩O)][ClO4] (2a - g, k - n, p, l′, l″) (P∼O: η11-P-coordinated; P∩O: η21-O,P-chelated). In the case of compounds 1o, 1k″, and 1o″, which are provided with less basic etherphosphanes, the halide-bridged dimers [(μ1-X)Pd(P∼O)2]2[ClO4]2 (3o, k″, o″) are obtained. Temperature-dependent 31P{1H}1-NMR spectra of the fluxional complexes 2a - g, k - n, p, l′, l″ lead to δG≢ values. By using a modified version of DNMR5, computer-generated spectra of 2a, b, f, k, l, p, l′, l″ were obtained and fitted to the experimental spectra. Graphic application of the Eyring equation to the kinetic data afforded the thermodynamic parameters δH≢, δS≢, and δG≢. The δS≢ values are in agreement with an associative exchange mechanism for 2a, b, f, l, p, l′, l″ and with a dissociative exchange mechanism for 2k, 2k and 3o crystallize in the monoclinic and triclinic space group P21/c and P&1marc; with Z=4 and Z=2, respectively.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19931260608
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  • 5
    Electronic Resource
    Electronic Resource
    Darstellung und Eigenschaften von und Reaktionen mit metallhaltigen Heterocyclen, LXXVI Regioselektive Cyclocotrimerisierung einer Thiophosphinit-Einheit mit Methylpropinoat (1991)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 1985-1988 
    Details
    ISSN: 0009-2940
    Keywords: Cyclocotrimerization ; Regioselectivity ; Thiophene ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Metal-Containing Heterocycles: Preparation, Properties, Reactions, LXXVI. - Regioselective Cyclocotrimerization of a Thiophosphinito Unit with Methyl PropynoateThe P = S function of (η2-PCy2=S)Mn(CO)4 (1) undergoes a regiospecific cyclocotrimerization with methyl propynoate to give the bicyclic compound 3. Oxidation of 3 with (NH4)2[Ce(NO3)6] results in the formation of the thiophene 4. Compound 3 was characterized on the basis of MS, IR, 31P{1H}-, 1H-, 13C{1H}-NMR spectra and with a 2D-H,C-COSY experiment.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19911240917
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  • 6
    Electronic Resource
    Electronic Resource
    Trägerfixierte Organometallkomplexe, III. Polysiloxan-gebundene (Ether-phosphan)ruthenium(II)-Komplexe und ihre CP-MAS-NMR-spektroskopische CharakterisierungHerrn Professor Wolfgang Beck zum 60. Geburtstag gewidmet. (1992)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 125 (1992), S. 2385-2390 
    Details
    ISSN: 0009-2940
    Keywords: Ether-phosphanes ; Ruthenium complexes ; Polysiloxane matrices ; CP-MAS NMR ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Carrier-Bound Organometallic Complexes, III[1]. - Polysiloxane-Bound (Ether-phosphane)ruthenium(II) Complexes and Their CP-MAS NMR-Spectroscopic CharacterizationThe reaction of the functionalized ether-phosphane ligand CH3O(CH2)2P(Ph)(CH2)3Si(OMe)3 (1c) with Cl2Ru(PPh3)3 (2) and HRuCl(CO)(PPh3)3 (3) results in the formation of the mono-chelated (ether-phosphane)ruthenium(II) complex Cl2Ru(P∼O)2(P∼O) (4c) and the hydride HRuCl(CO)(P∼O)3 (5c) (P∼O: η1-P-coordinated; P∼O: η2-O∼P-coordinated). Compounds 4c and 5c are polycondensated to the corresponding polysiloxane-bound complexes 4c′ and 5c′. 31P-chemical shifts of the immobilized species 4c′ and 5c′ in the solid-state CP-MAS NMR spectra are compared with those of the 31P{1H}-NMR spectra of monomeric complexes 4b, c and 5b, c with the ligands CH3O(CH2)2P(Ph)(CH2)3SiMe3 (1b) and 1c in solution. No change in the structure between the monomeric and polymeric species could be observed. According to 29Si CP-MAS NMR-spectroscopic investigations the polysiloxane chains are connected by ruthenium complexes to a network with favourable properties. The chelated polysiloxane-bound red complex 4c′ adds CO in the solid state to give quantitatively yellow all-trans-Cl2Ru(CO)2(P∼O)2 (6c′). In the presence of carbon monoxide there is an equilibrium between 5c′ and HRuCl(CO)2(P∼O)2 (7c′) which was also found in solution for 5b, c and 7b, c. The reactions indicate that the chemistry of polysiloxane-bound ether-phosphane complexes can well be compared with the chemistry in solution. 31P CP-MAS NMR spectra of the complexes 4c′ and 5c′ are strongly dominated by a chemical shift anisotropy which shows a fingerprint pattern both for monomeric crystalline complexes 4a, 5a [containing ligand Ph2P(CH2)2OCH3 (1a)] and polysiloxane-bound phosphane complexes 4c′ and 5c′.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19921251110
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  • 7
    Electronic Resource
    Electronic Resource
    Neuartige basische Liganden für die homogenkatalytische Methanolcarbonylierung, VI. Die Komplexchemie mehrzähniger (Tetrahydrofurfuryl)phosphane und ihr Einfluß auf die Selektivität und den Umsatz bei der Ethanolsynthese aus Methanol (1986)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 119 (1986), S. 2616-2630 
    Details
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Novel Basic Ligands for the Homogeneous Catalytic Methanol Carbonylation, VI. The Complex Chemistry of Multidentate (Tetrahydrofurfuryl)phosphanes and their Influence on the Selectivity and Conversion for the Synthesis of Ethanol from MethanolThe P,O ligands Ph2PCH2C4H7O (2) and PhP(CH2C4H7O)2 (3) react with (OC)5 MTHF (1a,b) [M=Mo (a), W (b)] to give the pentacarbonylmetal complexes 4b and 5a,b, respectively [eq. (1) and (2)]. Irradiation of 4b, 5a,b and the already known 4a in ether affords the kinetic unstable tetracarbonylmetal complexes (OC)4 MPPh2CH2C4H7O (6a,b) and (OC)4 MPPh(CH2C4H7O)2 (7a,b) with a bidentate function of 2,3 in each case via phosphorus and oxygen. With CO the reactions are reversible without separation of 2, 3 from the core of the complex [eq. (3) and (4)]. From Mo(CO)6 and 2 trans-(OC)4Mo (PPh2CH2C4H7O)2 (trans-8a) is formed which is rearranged to cis-8a via an “opening and closing mechanism” with participation of 2 and the labile Mo—O bond [eq. (5)]. The scission of the W—O bonds in 6b, 7b succeeds also with P(OMe)3 with formation of (OC)4 W[P(OMe)3]PPh2CH2C4H7O (9b) and (OC)4W[P(OMe)3] PPh(CH2C4H7O)2 (10b) [eq. (6)]. The different bonding conditions in 4-7 result from the IR, 31P{1H}, 13C{1H}, and 1H NMR spectra. The influence of 2 and 3 on the homologation of methanol to ethanol was investigated using cobalt as a component of the catalyst and iodine as a promotor. Dependent on the ratio of the synthesis gas, with 2 and equal catalyst composition in good selectivity either ethanol or methyl acetate is formed with conversions of 50 to 70%. The catalyst combination survives several cycles intact.
    Notes: Die P,O-Liganden Ph2PCH2C4H7O (2) und PhP(CH2C4H7O)2 (3) reagieren mit (OC)5 MTHF (1a,b) [M=Mo (a), W (b)] zu den Pentacarbonylmetall-Komplexen 4b bzw. 5a,b [Gl. (1) und (2)]. Bestrahlung von 4b, 5a,b und bereits bekanntem 4a in Ether liefert die kinetisch instabilen Tetracarbonylmetall-Komplexe (OC)4MPPh2CH2C4H7O (6a,b) und (OC)4MPPh(CH2C4H7O)2 (7a,b) mit jeweils zweizähniger Funktionsweise von 2, 3 über Phosphor und Sauerstoff. Mit CO sind die Reaktionen reversibel, ohne daß 2, 3 vom Komplexrumpf abgetrennt werden [Gl. (3) und (4)]. Aus Mo(CO)6 und 2 bildet sich trans-(OC)4 Mo(PPh2CH2C4H7O)2 (trans-8a), das sich über einen „äuf- und Zuklappmechanismus“ unter Beteiligung von 2 und der labilen Mo—O-Bindung in cis-8a umlagert [Gl. (5)]. Die Lösung der W—O-Bindung in 6b, 7b gelingt auch mit P(OMe)3 unter Bildung von (OC)4 W[P(OMe)3]PPh2CH2C4H7O (9b) und (OC)4W[P(OMe)3] PPh(CH2C4H7O)2 (10b) [Gl. (6)]. Die unterschiedlichen Bindungsverhältnisse in 4-7 ergeben sich aus den IR-, 31P{1H}-, 13C{1H}- und 1H-NMR-Spektren. Der Einfluß von 2 und 3 auf die Homologisierung von Methanol zu Ethanol wurde untersucht unter Verwendung von Cobalt als Katalysatormetall und lod als Promotor. In Abhängigkeit vom Synthesegasverhältnis erhält man mit 2 und gleicher Katalysatorzusammensetzung in guter Selektivität entweder Ethanol oder Methylacetat bei Umsätzen von 50 bis 70%. Das Katalysatorgemisch übersteht mehrere Zyklen unbeschadet.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19861190819
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  • 8
    Electronic Resource
    Electronic Resource
    Komplexchemischer Aufbau cyclischer 1,2-Dithiolato-Liganden mit dem nido-Cluster [(CO)3FeS]2.  -  Molekülstruktur und partielle S-Oxidation von Hexacarbonyl(μ2-cis-1,2-cyclohexandithiolato-S,S)dieisen (1990)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 1821-1826 
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    ISSN: 0009-2940
    Keywords: Disulfido clusters ; [2+2] Cycloadditions ; 1,2-Dithiolato ligands, cyclic ; Iron complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Complex-Chemical Synthesis of Cyclic 1.2-Dithiolato Ligands with the nido Cluster [(CO)3,FeS]2.  -  Molecular Structure and Partial S-Oxidation of Hexacarbonyl(μ2,-cis-1,2-cyclohexanedithiolato-S,S)diironThe cyclic alkenes, dienes, and trienes C6H10, C8C14, C5H6, C8C12 and C7H8 are inserted into the S-S bond of the nido cluster [(CO)3FeS]2 (1) by photochemically induced [2+2] cycloaddition reactions to give the complexes 2-6; thus, saturated and unsaturated cyclic 1,2-dithiolato ligands can be selectively built onto the complex in a μ2-bridging fashion. According to an X-ray structure analysis, the μ2-1,2-cyclohexanedithiolato-S,S complex 2a with the pseudotetrahedral skeleton [(CO)3FeS]2 crystallizes in the monoclinic space group P21/c; the S2 moiety is bridged by cyclohexane with 1,2-cis configuration. As an example, the partial S oxidation of 2a was carried out, leading to 2b by selective transformation of one thiolato into a sulfenato function.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19901230911
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  • 9
    Electronic Resource
    Electronic Resource
    Intramolecular Metalation of C—H Bonds with {cis,cis-1,3,5-Tris[(diphenylphosphino)methyl]cyclohexane}rhodium(I) Chloride (1990)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 1827-1831 
    Details
    ISSN: 0009-2940
    Keywords: Tripodal phosphane ligand ; Rhodium complexes ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The novel tridentate ligand cis,cis-1,3,5-tris[(diphenylphosphino)methyl]cyclohexane (6) has been synthesized and treated with [Rh(COD)Cl]2. Intramolecular metalation of a C—H bond of the cyclohexane ring occurs (7). Studies with D2 gas and 6[D6] prove that axial and equatorial C—H bonds are metalated and that a mutual exchange occurs in this process. Replacement of the Cl- by the SbF-6 anion in 7 results in a reduced interaction between the metal and the C—H bond (8). 7 reacts with CO to form the carbonyl 9 where no such interaction is observed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19901230912
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