Thermal reaction of 1â:â1 mixtures of the RuCl2(PPh3)3 and phosphinoimine R2PNCPh2 (R = Ph, iPr, Me) at 140 °C results in isolation of the dimeric species [RuCl(μ-Cl)(PPh3)(C6H4(PPh2)C(Ph)NH)]2 (R = Ph 1, iPr 2, Me 3) containing phosphineâimine chelating ligands. Subsequent reaction of 1 and 3 with one equivalent of pyridine at room temperature give RuCl2(PPh3)(py)(C6H4(PR2)C(Ph)NH) (R = Ph 4, Me 5). Excess pyridine reacts with 2 to give a mixture of the cis and trans-isomers of RuCl2(py)2(C6H4(PiPr2)C(Ph)NH) 6 and 7 respectively. Treatment of 5 with excess PPh3 affords RuCl2(PPh3)2(C6H4(PMe2)C(Ph)NH) 8. Aspects of the mechanism of the thermal rearrangements of the phosphinoimine to the phosphineâimine ligands are considered and the isolation of RuCl2(Ph2PNCPh2)(SIMes)(CHPh) 9 and RuCl2(PPh3)2(HNC(Ph)C6H4) 10 provide support for a proposed mechanism involving a intermediate containing a Ru-bound metallated aryl-imine fragment.
RuCl2(PPh3)3 和膦
亚胺 R2
PNCPh2 (R = Ph, iPr, Me) 的 1-:-1 混合物在 140 °C 下发生热反应,分离出二聚体 [RuCl(μ-Cl) (PPh3)(
C6H4(PPh2)C(Ph)NH)]2 (R = Ph 1, iPr 2, Me 3)含有膦·
亚胺螯合
配体。随后,1和3与一当量
吡啶在室温下反应,得到RuCl2(PPh3)(py)( (PR2)C(Ph)NH)(R = Ph 4, Me 5)。过量的
吡啶与2反应,分别得到RuCl2(py)2( (PiPr2)C(Ph)NH) 6 和7的顺式和反式异构体的混合物。用过量的 PPh3 处理 5,得到 RuCl2(PPh3)2( (PMe2)C(Ph)NH) 8。考虑了膦
亚胺与膦-
亚胺配体的热重排机制以及 RuCl2 的分离(Ph2
PNCPh2)(SIMes)(CHPh) 9 和RuCl2(PPh3)2(HNC(Ph) ) 10 为涉及含有Ru结合
金属化芳基
亚胺片段的中间体的拟议机制提供了支持。