E−H Bond Activation Reactions (E = H, C, Si, Ge) at Ruthenium: Terminal Phosphides, Silylenes, and Germylenes
作者:Ayumi Takaoka、Arjun Mendiratta、Jonas C. Peters
DOI:10.1021/om900216u
日期:2009.7.13
anchoring silyl group affords the complexes [SiPPh3]RuR (R = Me (2), CH2Ph (4), PPh2 (5), PiPr2 (6)). Complexes 2, 4, and 5 are thermally unstable. Complexes 2 and 4 decay to the cyclometalated complex [SiPPh2P′Ph]Ru (3), whereas complex 5 decays to the cyclometalated phosphine adduct [SiPPh2P′Ph]Ru(PHPh2) (7). Complex 3 is found to effect E−H (E = H, C, Si, Ge) bond activation of substrates such as secondary
在四齿三脚架三(膦基)甲硅烷基配体的锚定甲硅烷基相反的钌中心上放置强反型配体,[SiP Ph 3 ] -([SiP Ph 3 ] - = tris(2-(二苯基膦基)苯基)甲硅烷基),已经被探索。将烷基或末端磷化物配体反式安装到锚定的甲硅烷基上可得到复合物[SiP Ph 3 ] RuR(R = Me(2),CH 2 Ph(4),PPh 2(5),P i Pr 2(6))。复合物2,4,和5是热不稳定的。配合物2和4衰变到环金属化配合物[SiP的博士2 P'博士]钌(3),而复杂的5个衰变到环金属膦加合物[SiP的博士2 P'博士]钌(PHPh 2)(7)。发现配合物3会影响底物(例如仲硅烷和锗烷)的E-H(E = H,C,Si,Ge)键活化,从而产生结构异常的亚甲硅烷基配合物[SiP Ph 3] Ru(H)(SiRR')(R = R'= Ph(10a),R = Ph R'= Me(10b))和亚甲基配合物[SiP