A Stable Silylene in a Reactive Environment: Synthesis, Reactivity, and Silicon Extrusion Chemistry of a Coordinatively Unsaturated Ruthenium Silylene Complex Containing Chloride and η<sup>3</sup>-P−C−P Ligands
作者:Dino Amoroso、Michael Haaf、Glenn P. A. Yap、Robert West、Deryn E. Fogg
DOI:10.1021/om0101801
日期:2002.2.1
4 equiv of the stable silylene 1,3-di-tert-butyl-1,3,2-diazasilol-2-ylidene (SiLN2) yields coordinatively unsaturated RuCl(η3-dcypb)(SiLN2) (2). Complex 2 is a rare example of a trans-spanning diphosphine complex, this geometry resulting from an unprecedented attack of the metal on the tetramethylene ligand backbone. X-ray and solid-state 31P NMR and IR analysis reveal an agostic interaction between
[(dcypb)ClRu(μ-Cl)3 Ru(dcypb)(N 2)](1)与4当量的稳定亚甲硅1,3-二叔丁基-1,3,2-二氮杂硅烷基-的反应咪唑-2-亚基(SIL ñ 2)得到配位不饱和的RuCl(η 3 -dcypb)(SIL ñ 2)(2)。配合物2是跨跨二膦配合物的罕见实例,这种几何形状是由于金属对四亚甲基配体主链的空前攻击而导致的。透视和固态31 P NMR和IR分析显示金属和亚甲硅烷卜之间的抓氢键吨团体。在溶液中,只有在低温下才能观察到这种相互作用。的反应2用H 2含微量ħ 2个ö产量硅氧烷二聚物[L Ñ 2的Si(H)] 2 ö 3和钌氢化物-H 2加合物[(dcypb)(H)的Ru(μ-Cl)的2(μ -H)Ru(dcypb)(H 2)](4)。尝试分离4导致分解产物5 [[dcypb)(H)Ru(μ-Cl)3 Ru(dcypb)(N 2)]意外结晶。对5的X射线分析表