The pro-ligands 1,8-bis(di-R-phosphinomethyl)-2,3-dihydroperimidine (RHPm, R = phenyl, cyclohexyl) react with [RhCl(CE)(PPh)] (E = O, S) to afford the bimetallic complexes [RhCl(CE)(μ-RHPm)] (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-PhHPm)] with KC results in the bimetallic rhodium(0) complex, [Rh(μ-CO)(PhHPm)], 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)]BF. Treatment of [RhCl(CO)(PhHPm)] with lithium (trimethylsilyl)acetylide provides another bimetallic species, [Rh(CCSiMe)(CO)(PhHPm)], however heating this species does not proceed cleanly to the monomeric NHC complex, [Rh(CCSiMe)(CO)(PhPm)] which may however be obtained from [RhCl(RPm)] and LiCCSiMe.
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