Hydrodealkoxylation reactions of silyl ligands at platinum: reactivity of SiH<sub>3</sub>and SiH<sub>2</sub>Me complexes
作者:Cathérine Mitzenheim、Thomas Braun、Reik Laubenstein、Beatrice Braun、Roy Herrmann
DOI:10.1039/c5dt04923g
日期:——
intermediate complexes [Pt(H)SiMe(OEt)2}(dcpe)] (5), [PtSiMe(OEt)2}2(dcpe)] (6), [PtSiHMe(OEt)}2(dcpe)] (7) and [PtSiHMe(OMe)}2(dcpe)] (8) were detected. Treatment of the complex 1 with an excess of dichloromethylsilane yields the bis(silyl) complex [Pt(SiMeCl2)2(dcpe)] (9). The hydrido silyl complex [Pt(H)(SiMeCl2)(dcpe)] (10) was identified as an intermediate. The reactions of the complexes [Pt(SiH3)2(dcpe)]
铂(II)配合物[Pt(H)2(dcpe)](1 ; dcpe = 1,2-双(二环己基膦基)乙烷)与过量的二烷氧基甲基硅烷(HSiMe(OR)2 ; R = Me,Et )通过加氢脱烷氧基化反应得到双(甲硅烷基)配合物[Pt(SiH 2 Me)2(dcpe)](3)和三烷氧基甲基硅烷。甲硅烷基配体的这些重排涉及Si–O键的活化。烷氧基部分与结合硅的氢原子的交换是逐步发生的。中间配合物[Pt(H)SiMe(OEt)2 }(dcpe)](5),[Pt SiMe(OEt)2 } 2(dcpe)](6),检测到[Pt SiHMe(OEt)} 2(dcpe)](7)和[Pt SiHMe(OMe)} 2(dcpe)](8)。用过量的二氯甲基硅烷处理配合物1产生双(甲硅烷基)配合物[Pt(SiMeCl 2)2(dcpe)](9)。氢化甲硅烷基络合物[Pt(H)(SiMeCl 2)(dcpe)]