Structure and Reactivity of [Ru-Al] and [Ru-Sn] Heterobimetallic PPh-Based Complexes.

Treatment of [Ru(PPh)(CHPPh)H][Li(THF)] with AlMeCl and SnMeCl leads to elimination of LiCl and CH and formation of the heterobimetallic complexes [Ru(CHPPh){PPhCHAlMe(THF)}H] and [Ru(PPh)(CHPPh)(PPhCHSnMe)] , respectively. The pathways to and have been probed by variable temperature NMR studies, together with input from DFT calculations. Complete reaction of H occurs with at 60 °C and with at room temperature to yield the spectroscopically characterized trihydride complexes [Ru(PPh){PPhCHAlMe}H] and [Ru(PPh){PPhCHSnMe}H] . In the presence of CO, forms the acylated phosphine complex, [Ru(CO)(C(O)CHPPh)(PPhCHSnMe)] , through a series of intermediates that were identified by NMR spectroscopy in conjunction with CO labeling. Complex undergoes addition and substitution reactions with the N-heterocyclic carbene 1,3,4,5-tetramethylimidazol-2-ylidene (IMe) to give [Ru(IMe)(PPhCH)(PPhCHSnMe)] , which converted via rare N-Me group C-H activation to [Ru(IMe)(PPh)(IMe)'(PPhCHSnMe)] upon heating at 60 °C and to a mixture of [Ru(IMe)(IMe)'(PPhCHSnMe)] and [Ru(PPh)(PPhCH)(IMe-SnMe)'] at 120 °C.