Ruthenium Complexes Containing Two Ru−(η<sup>2</sup>-Si−H) Bonds: Synthesis, Spectroscopic Properties, Structural Data, Theoretical Calculations, and Reactivity Studies
作者:Fabien Delpech、Sylviane Sabo-Etienne、Jean-Claude Daran、Bruno Chaudret、Khansaa Hussein、Colin J. Marsden、Jean-Claude Barthelat
DOI:10.1021/ja990199j
日期:1999.7.1
The bis(dihydrogen) complex RuH2(H2)2(PCy3)2 (1) reacts with the disilanes (R2SiH)2X to produce the dihydride complexes [RuH2(η2-HSiR2)2X}(PCy3)2] (with R = Me and X = O (2a), C6H4 (3), (CH2)2 (4), (CH2)3 (5), OSiMe2O (6)) and R = Ph, X = O (2b)). In these complexes, the bis(silane) ligand is coordinated to ruthenium via two σ-Si−H bonds, as shown by NMR, IR, and X-ray data and by theoretical calculations
双(二氢)配合物 RuH2(H2)2(PCy3)2 (1) 与乙硅烷 (R2SiH)2X 反应生成二氢化物配合物 [RuH2(η2-HSiR2)2X}(PCy3)2](其中 R = Me and X = O (2a), C6H4 (3), (CH2)2 (4), (CH2)3 (5), OSiMe2O (6)) 和 R = Ph, X = O (2b))。在这些配合物中,双(硅烷)配体通过两个 σ-Si-H 键与钌配位,如 NMR、IR 和 X 射线数据以及理论计算所示。3、4和6通过X射线衍射表征。在游离乙硅烷中,Si-H 键距和 JSi-H 值分别约为 1.49 A 和 200 Hz,而在新配合物中,值分别在 1.73-1.98 A 和 22-82 Hz 范围内σ-Si-H 键。非键合 H···Si 相互作用的重要性,它控制观察到的两个庞大的 PCy3 配体的顺式几何结构,X 射线数