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  • 1
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Mixed Ligand Complexes of Nickel(0) and Cobalt(I) with the Anionic Ligands E(C6H5)3- (E = Ge, Sn, Pb)Complexes of the general formula MINi(PPh3)3(EPh3)(THF)x (E = Ge[Ia], Sn[Ib], Pb[Ic]) and MI3Ni(PPh3)(EPh3)3(THF)x (E = Ge[IIa], Sn[IIb]) are formed from (Ph3P)2Ni(C2H4) by substitution with MIEPh3. The analogous complexes of the ligand SiPh3- could not be prepared, because of the formation of SiPh4 from LiSiPh3 and coordinated PPh3. Attempts to synthesize a nickel(II) complex of the ligand SnPh3- had no success, only possible decomposition products of these compounds, like (nBu2PPh)2NiII(Ph)Cl and NaxNi°(PPh3)4-x(SnP4)x(THF)Y, were isolated. NaCoI(PPh3)2(SnPh3)2(THF)7 (IV) was prepared by the reaction of Co(PPh3)3Cl and NaSnPh3.1H-NMR and 119Sn Mössbauer spectra show a higher donor action of SnPh3- in IIb than in Ib. This causes a stronger π-back donation Ni → P in the case of IIb. IV is a paramagnetic compound, the vis-spectrum is discussed using simple crystal field theory.
    Notes: (Ph3P)2Ni°(C2H4) reagiert mit Verbindungen des Typs MIEPh3 unter Substitution zu Gemischtligand-Komplexen MINi°(PPh3)3(EPh3)(THF)x (E = Ge[Ia], Sn[Ib], Pb[Ic]) bzw. MI3 Ni°(PPh3)3(EPh3) (THF)x (E = Ge[IIa], Sn[IIb]). Analoge Komplexe mit dem Liganden SiPh3- konnten nicht isoliert werden, da LiSiPh3 mit komplex gebundenem PPh3 zu SiPh4 reagiert. Versuche zur Synthese von Nickel(II)-Komplexen des Liganden SnPh3- blieben ohne Erfolg, es wurden nur mögliche Zersetzungsprodukte dieser Verbindungen isoliert [(nBu2PPh)2Ni(Ph)Cl und NaxNi(PPh3)4-X(SnPh3)x(THF)Y]. Die Umsetzung von (Ph3P)3CoCl mit NaSnPh3 führt zu NaCoI (PPh3)2(SnPh3)2(THF)7.Aus den 1H-NMR- und den 119Sn-Mößbauerspektren ergibt sich, daß die Donatorwirkung der Liganden SnPh3- beim Übergang von Ib zu IIb ansteigt. Daraus resultiert für IIb eine im Vergleich zu Ib höhere π-Backdonation. IV ist paramagnetisch, das VIS-Spektrum kann auf der Basis der Kristallfeldtheorie erklärt werden.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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