C–H activation in bimetallic rhodium complexes to afford N-heterocyclic carbene pincer complexes

Abstract

The pro-ligands 1,8-bis(di-R-phosphinomethyl)-2,3-dihydroperimidine (RH₂Pm, R = phenyl, cyclohexyl) react with [RhCl(CE)(PPh₃)₂] (E = O, S) to afford the bimetallic complexes [RhCl(CE)(μ-RH₂Pm)]₂ (E = O, S). Upon heating, these species undergo double C–H activation to afford the N-heterocyclic carbene (NHC) pincer complexes [RhCl(RPm)]. Reduction of [RhCl(CO)(μ-PhH₂Pm)]₂ with KC₈ results in the bimetallic rhodium(0) complex, [Rh(μ-CO)(PhH₂Pm)]₂, with a formal Rh–Rh bond and a hydrogen-bonding interaction between rhodium and the central methylene group (C–H⋯Rh = 2.802 Å). Upon treatment with tritylium, ferrocenium or triphenylcyclopropenium tetrafluoroborates this species undergoes double C–H activation to afford a mononuclear NHC pincer complex salt, [Rh(CO)(PhPm)]BF₄. Treatment of [RhCl(CO)(PhH₂Pm)]₂ with lithium (trimethylsilyl)acetylide provides another bimetallic species, [Rh(CCSiMe₃)(CO)(PhH₂Pm)]₂, however heating this species does not proceed cleanly to the monomeric NHC complex, [Rh(CCSiMe₃)(CO)(PhPm)] which may however be obtained from [RhCl(RPm)] and LiCCSiMe₃.