Structure and Reactivity of [Ru–Al] and [Ru–Sn] Heterobimetallic PPh(3)-Based Complexes

[Image: see text] Treatment of [Ru(PPh(3))(C(6)H(4)PPh(2))(2)H][Li(THF)(2)] with AlMe(2)Cl and SnMe(3)Cl leads to elimination of LiCl and CH(4) and formation of the heterobimetallic complexes [Ru(C(6)H(4)PPh(2))(2){PPh(2)C(6)H(4)AlMe(THF)}H] 5 and [Ru(PPh(3))(C(6)H(4)PPh(2))(PPh(2)C(6)H(4)SnMe(2))] 6, respectively. The pathways to 5 and 6 have been probed by variable temperature NMR studies, together with input from DFT calculations. Complete reaction of H(2) occurs with 5 at 60 °C and with 6 at room temperature to yield the spectroscopically characterized trihydride complexes [Ru(PPh(2))(2){PPh(2)C(6)H(4)AlMe}H(3)] 7 and [Ru(PPh(2))(2){PPh(2)C(6)H(4)SnMe(2)}H(3)] 8. In the presence of CO, 6 forms the acylated phosphine complex, [Ru(CO)(2)(C(O)C(6)H(4)PPh(2))(PPh(2)C(6)H(4)SnMe(2))] 9, through a series of intermediates that were identified by NMR spectroscopy in conjunction with (13)CO labeling. Complex 6 undergoes addition and substitution reactions with the N-heterocyclic carbene 1,3,4,5-tetramethylimidazol-2-ylidene (IMe(4)) to give [Ru(IMe(4))(2)(PPh(2)C(6)H(4))(PPh(2)C(6)H(4)SnMe(2))] 10, which converted via rare N-Me group C–H activation to [Ru(IMe(4))(PPh(3))(IMe(4))′(PPh(2)C(6)H(4)SnMe(2))] 11 upon heating at 60 °C and to a mixture of [Ru(IMe(4))(2)(IMe(4))′(PPh(2)C(6)H(4)SnMe(2))] 12 and [Ru(PPh(3))(PPh(2)C(6)H(4))(IMe(4)-SnMe(2))′] 13 at 120 °C.