摘要:
The oxidative addition of I-2, PhCH2Br and MeI with [Pt(CH2SiMe3)(2)(DPK)], 1, DPK = di-2-pyridyl ketone, occurred with trans stereochemistry to give [PtI2(CH2SiMe3)(2)(DPK)], [PtBr(CH2Ph)(CH2SiMe3)(2)(DPK)] and [PtIMe(CH2SiMe3)(2)(DPK)], respectively. Complex 1 reacted with acids HX (X = Cl or CF3CO2) to give initially the hydridoplatinum complexes [PtHX(CH2SiMe3)(2)(DPK)], but these complexes were thermally unstable and decomposed largely by alpha-silyl migration to give compounds such as [PtX(SiMe3)Me-2(DPK)], as determined by monitoring the reactions by NMR at low temperature. With excess acid, HX, at room temperature, the products were largely [PtX2(DPK)], CH4 and Me3SiX with Me4Si as a minor product only. The mechanism of the easy Si-CH2 bond cleavage is discussed. (C) 2010 Elsevier B. V. All rights reserved.