Facile Formation of Rare Terminal Chalcogenido Germanium Complexes with Alkylamidinates as Supporting Ligands

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• 作者：Stephen R. Foley ; Corinne Bensimon ; and Darrin S. Richeson
• 刊名：Journal of the American Chemical Society
• 出版年：1997
• 出版时间：October 29, 1997
• 年：1997
• 卷：119
• 期：43
• 页码：10359 - 10363
• 全文大小：172K
• 年卷期：v.119,no.43(October 29, 1997)
• ISSN：1520-5126

文摘

The first characterized amidinate complexes of Ge havebeen prepared using alkylamidinates as ancillaryligands. Spectroscopic and structural characterization of the twocomplexes, (CyNC(Me)NCy)₂Ge^II(1) and(CyNC(^tBu)NCy)₂Ge^II(2) (Cy = cyclohexyl), revealed that the Ge coordinationgeometry is distorted tetrahedral inwhich one of the vertices is occupied by a lone pair of electrons.Both 1 and 2 exhibited one bidentate andonemonodentate ("dangling") ligand. Rapid oxidative addition ofchalcogen atom sources (styrene sulfide and Se) tothese complexes resulted in a series of rare terminal chalcogenidocomplexes with the formulas (CyNC(R)NCy)₂Ge=Ch [R = Me, Ch = S (3),Se(4); R = ^tBu, Ch = S(5), Se(6)]. The spectroscopic dataand X-ray structureof 6 revealed a terminal Ge=Se complex. Mixedamidinato-amido analogues were similarly obtained. Forexample,[(CyNC(R)NCy)Ge^II[N(SiMe₃)₂](R = Me, ^tBu) react to yield the correspondingterminal chalcogenido complexes.In the case of[(CyNC(Me)NCy)Ge^II[N(SiMe₃)₂]Se(10), a crystallographic study confirmed the presence of aterminalGe=Se bond.