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  • Articles: DFG German National Licenses  (72)
  • 1980-1984  (72)
  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Organometallics 2 (1983), S. 1550-1554 
    ISSN: 1520-6041
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of the American Chemical Society 105 (1983), S. 3806-3811 
    ISSN: 1520-5126
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1520-6041
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1520-6041
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Organometallics 3 (1984), S. 1906-1909 
    ISSN: 1520-6041
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Monatshefte für Chemie 111 (1980), S. 1233-1244 
    ISSN: 1434-4475
    Keywords: Metallocycles ; Organometallic compounds of do and d10 metals ; Phosphane boranes ; Phosphorus Ylides ; Ylide complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Dehydrohalogenation and metallation of boranato-bis-trimethylphosphonium salts (1), using two equivalents of a lithiumalkyl in tetrahydrofuran, leads to a solvated organolithium reagent H2B[(CH3)2PCH2]2Li (3) which can be converted into a 1:1n1-complex with tetramethylethylenediamin (4).3 reacts with anhydrous metal(II) halides to form spirocyclic coordination compounds of the type H2B[(CH3)2PCH2]2 M[CH2P(CH3)2]2BH2 (5–9,M=Be, Mg, Zn, Cd, Hg). The reaction of [(CH3)3PBH2P(CH3)3]Br (1) with lithium tetramethylmetalates Li[M(CH3)4],M=Al, Ga, on heating in the absence of a solvent affords the metallocycles H2B[(CH3)2PCH2]2 M(CH3)2 (10, 11) with evolution of methane. The products can be sublimed from the reaction mixture. The proposed structures of the new compounds, with tetrahedrally coordinated central atoms and strong covalent metal-carbon interactions, are supported by mass, IR and1H,7Li,11B,13C, and31P NMR spectra. Compound9 represents a rare case of a tetracoordinate organomercurial, compound5 is the first nonionic tetraalkylberyllate.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 113 (1980), S. 902-911 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Structure of Crystalline Sodiumorganic Compounds from Phosphorus YlidesThe two ylides (C6H5)2P - CH = P(C6H5)2 - CH2C6H5 (4) and C6H5CH2(C6H5)2P = CH - P(C6H5)2 = CHC6H5 (5) are synthesized from (C6H5)2P - CH2 - P(C6H5)2 (1) via their corresponding benzylphosphonium salts 2 und 3. The double ylide 5 exists solely in the above conjugated form, in contrast to most other R3PCPR3 molecules, where the cumulated isomer is preferred. There is rapid proton scrambling between benzyl and benzylidene hydrogens as detected by NMR spectroscopy. 4 and 5 react with NaNH2 to form coloured sodium complexes, in which the metal is bonded via the benzylide functions. NMR spectra indicate a symmetrical coordination site for Na+ above the benzylidene ring. The coordination sphere is completed by ether and/or tetrahydrofurane molecules. In an X-ray structure analysis of 6, which crystallizes with one (C2H5)2O and one C4H8O molecule, the details of the structure were elucidated. A 23Na NMR spectrum confirms the extremely asymmetrical array of ligands at the metal center. In the e.i. mass spectrum the sodium-containing molecular ion is observed.
    Notes: Aus (C6H5)2P — CH2 — P(C6H5)2 (1) werden über die zugehörigen Benzylphosphoniumsalze 2 und 3 die beiden Ylide (C6H5)2P — CH = P(C6H5)2 — CH2C6H5 (4) und C6H5CH2(C6H5)2P = CH — P(C6H5)2 = CHC6H5 (5) synthetisiert. Letzteres existiert im Gegensatz zu anderen R3PCPR3-Molekülen ausschließlich als konjugiertes Doppel-Ylid und zeigt raschen Protonenaustausch zwischen Benzyl-und Benzylidengruppe. 4 und 5 reagieren mit NaNH2 zu tieffarbigen Natriumkomplexen, in denen das Metall über die Benzylidfunktionen gebunden ist. NMR-Spektren zeigen eine symmetrische Bindung des Metalls an den Benzylidenring an. Die Koordinationssphäre des Na+ wird durch Ether- und/oder Tetrahydrofuranmoleküle ergänzt. Eine Röntgenstrukturanalyse von 6, das aus Ether mit je 1 Molekül Ether und Tetrahydrofuran kristallisiert, klärte Details der Bindungsverhältnisse in diesen neuen natriumorganischen Verbindungen. Das 23Na-NMR-Spektrum bestätigt die außerordentlich unsymmetrische Umgebung des Metalls. Im Massenspektrum wird das natriumhaltige Molekül-Ion beobachtet.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 113 (1980), S. 1145-1152 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese und eine Kristallstrukturanalyse von gemischten Bis(phosphino)methanid/Phosphonium-bis(methylid)-Komplexen des Nickels, Palladiums und PlatinsAus den Bis(diphenylphosphino)methanid-Komplexen des Typs {[(C6H5)2P]2CH}2M (M = Ni, Pd, Pt) und der äquivalenten Menge eines Ylids R2(CH3)P = CH2 (R = CH3, C2H5) wurden die drei Titelverbindungen {[(C6H5)2P]2CH}M[(CH2)2PR2] (5a - c) erhalten. Eine Röntgenbeugungsanalyse der Platinverbindung 5c ergab eine gemischte Chelatstruktur mit einem ebenen Bis(phosphino)methanid- und einem gefalteten Ylidring. Das mittlere C-Atom des Bis(phosphino)methanids unterhält keine direkten Kontakte zum Metall. Seine Abstände zu den P-Atomen deuten erheblichen Doppelbindungscharakter an. Ylidischer Doppelbindungscharakter wird auch in der Phosphonium-bis(methylid)-Gruppe beibehalten.
    Notes: From bis(diphenylphosphino)methanide complexes of the type {[(C6H5)2P]2CH}2M (M = Ni, Pd, Pt), and an equivalent amount of an ylide R2(CH3)P = CH2 (R = CH3, C2H5), the three title complexes {[(C6H5)2P]2CH}M[(CH2)2PR2] (5a - c) have been prepared. CH2[P(C6H5)2]2 is the by-product of the reaction. An X-ray diffraction study of the platinum compound 5c revealed a mixed chelate structure with a planar bis(phosphino)methanide and a folded ylide ring. The central carbon of the bis(phosphino)methanide is not in close contact with the metal. Its distances to the phosphorus atoms indicate significant double bond character, some of which is also retained in the phosphonium bis(methylide) group.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 113 (1980), S. 1646-1653 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cyclic μ-(4-Methylcyclohexadien-1-ylidenio)-bis[phosphanegold(I)] CationsArylation of α, ω-bis[(chloroaurio)diphenylphosphino]alkanes 1b - d using p-tolyllithium yields the binuclear tolylgold compounds [(p-CH3C6H4Au)P(C6H5)2]2[CH2]n with n = 2, 3, and 4 (2b - d). p-CH3C6H4AuP(CH3)3 was obtained similarly as an NMR reference compound. 2d is converted into the cation p-CH3C6H4[AuP(C6H5)2(CH2)2]2+ BF4- on treatment with HBF4 in diethyl ether, with elimination of toluene. The product is ascribed the cyclic structure 3d, based on NMR and 197Au Mößbauer data.
    Notes: Aus den α, ω-Bis[(chloroaurio)diphenylphosphino]alkanen 1b - d wurden durch Arylierung mit p-Tolyllithium die zweikernigen Tolylgoldverbindungen [(p-CH3C6H4Au)P(C6H5)2]2[CH2]n mit n = 2, 3 und 4 (2b - d) synthetisiert. Zusätzlich wurde p-CH3C6H4AuP(CH3)3 als NMR-Vergleichssubstanz hergestellt. 2d liefert bei der Behandlung mit etherischem HBF4 unter Abspaltung von Toluol das Kation p-CH3C6H4[AuP(C6H5)2(CH2)2]2+ BF4-, dem aufgrund der NMR-und 197Au-Mößbauer-Spektren die cyclische Struktur 3d zugeschrieben wird.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Eine neue Synthese und die Molekülstruktur von Trimethyl(silylmethylen)phosphoran durch Elektronenbeugung in der GasphaseTrimethyl(silylmethylen)phosphoran (1) entsteht in der Reaktion von H3SiCH2CH2Cl mit (CH3)3P=CH2 im Molverhältnis 1:2, wobei in einer β-Eliminierung C2H4 entwickelt und in einer Umylidierungsstufe [(CH3)4P]+Cl- gebildet wird. Die Molekülstruktur von (CH3)3P=CHSiH3 in der Gasphase wurde durch Elektronenbeugung bestimmt. Wichtigste Bindungslängen ra sind P—C = 180.7(8), P=C = 165.3(11) und Si—C = 185.2(20) pm. Die Winkel CPC der Trimethyl-phosphangruppe betragen 103.4(13)°, der Si—C = P-Winkel 123.4(8)°, in Einklang mit einer planaren Konfiguration am Ylid-C-Atom. Das Molekül besitzt eine Konformation, in der die Si—C-Bindung um 25° von der Position weggedreht ist, in der sie mit einer P—C-Bindung eclipsed steht. Die Amplitude der Drehschwingungen um die P—C-Bindung ist jedoch beträchtlich hoch.
    Notes: Trimethyl(silylmethylene)phosphorane (1) has been prepared in a reaction of H3SiCH2CH2Cl and (CH3)3P=CH2 in a molar ratio 1:2. C2H4 is evolved in a β-elimination process, followed by formation of [(CH3)4P]+Cl- in a transylidation step.  -  The molecular structure of (CH3)3P=CHSiH3 in the gas phase has been determined by electron diffraction. Principal bond lengths (ra) are: P—C = 180.7(8), P = C = 165.3(11), Si—C = 185.2(20) pm. The angles between the P—C(methyl) bonds are 103.4(13)° and the Si—C=P angle is 123.4(8)°, consistent with a planar configuration of the methylene carbon atom. The molecule adopts a conformation in which the Si—C bond is twisted 25° from a position in which it eclipses one P—C bond, but there is a large amplitude torsional vibration about the P—C bond.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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