Synthesis and Reactivity of the Pentacoordinate Organosilicon and-germanium Compounds Containing the C,P-Chelating ￥?-Carboranylphosphino Ligand [￥?-C2B10H10PPh2-C,P](CabC,P)

摘要

The synthesis of the intramolecular donor-stabilized silyl and germyl complexes of the type (CabC,P)MMe₂X (2a : M=Si, X = Cl; 2b : M = Ge, X =Cl;2c :M =Si, X=H) was achieved by the reaction of LiCabC,P(1) with Me₂SiClX and Me₂GeCl₂, respectively . The intramolecular M＄P interaction in 2a-2c is provided by 1H, 13C, 31P, and 29Si NMR spectroscopy. The salt elimination reaction of dichlorotetramethyldisilane and -digermance with 1 afforded the bis (ワ-carboranylphosphino) disilane and digermance [(CabC,P)MMe₂]₂ (4a : M =Si ; 4b : M= Ge). The oxidative addition reaction of 4a-4b with Pd₂(dba)₃·CHCl₃ afforded the bis(silyl)-and bis(germyl)-palladium complexes. The chloro-bridged dipalladium complexes were obtained by the reaction of 2a-2b with Pd₂(dba)₃·CHCl₃. The crystal structures of 5a and 7b were determined by X-ray structural studies.