bond. A similar reaction of L′ with [RhCl(PPh3)3] produces [RhCl(PPh3)(Ph2PO2CCHCHMe)], involving metal-promoted double-bond migration in the L′ ligand. Reaction of 2 mol of L per mol of rhodium produces [RhCl(PPh3)(Ph2POPPh2)] involving a metal-promoted disruption of the L ligand to bidentate tetraphenyldiphosphoxane. Reaction of [RhCl(PPh3)(Ph2POPPh2)] with TlPF6 produces [Rh(PPh3)2(Ph2POPPh2)][PF6]
在
三乙胺存在下,Ph 2 PCl与CH 2 CHCO 2 H和CH 2 CHCH 2 CO 2 H反应分别产生Ph 2 PO 2 CCH CH 2(L)和Ph 2 PO 2 CCH 2 CH CH 2(L') 。发现两者都经历进一步的分子间反应以产生Ph 2 PP(O)Ph 2。L与[RhCl(PPh 3)3 ]的反应,每1摩尔Rh 1摩尔L,生成[RhCl(PPh 3)L],然后还原为[RhCl(PPh 3)L)3 ](如果留在溶液中)。化合物[RhCl(PPh 3)L]含有通过
磷原子和双键配位的二齿L
配体。L'与[RhCl(PPh 3)3 ]的类似反应产生[RhCl(PPh 3)(Ph 2 PO 2 CCH CHMe)],涉及
金属在L'
配体中促进的双键迁移。每摩尔
铑2摩尔L的反应产生[RhCl(PPh 3)(Ph 2 P
OPPh 2)],该过程涉及
金属促进L
配体的破坏,从而使
四苯基二膦恶烷化。[RhCl(PPh