Bonding and reactivity of a pair of neutral and cationic heterobimetallic RuZn complexes

A combined experimental and computational study of the structure and reactivity of two [RuZn2Me2] complexes, neutral [Ru(PPh3)(Ph2PC6H4)2(ZnMe)2] (2) and cationic [Ru(PPh3)2(Ph2PC6H4)(ZnMe)2][BArF4] ([BArF4] = [B{3,5-(CF3)2C6H3}4]) (3), is presented. Structural and computational analyses indicate these complexes are best formulated as containing discrete ZnMe ligands in which direct Ru-Zn bonding is complemented by weaker Zn···Zn interactions. The latter are stronger in 2, and both complexes exhibit an additional Zn···Caryl interaction with a cyclometalated phosphine ligand, this being stronger in 3. Both 2 and 3 show diverse reactivity under thermolysis and with Lewis bases (PnBu3, PCy3, and IMes). With 3, all three Lewis bases result in the loss of [ZnMe]+. In contrast, 2 undergoes PPh3 substitution with PnBu3, but with IMes, loss of ZnMe2 occurs to form [Ru(PPh3)(C6H4PPh2)(C6H4PPhC6H4Zn(IMes))H] (7). The reaction of 3 with H2 affords the cationic trihydride complex [Ru(PPh3)2(ZnMe)2(H)3][BArF4] (12). Computational analyses indicate that both 12 and 7 feature bridging hydrides that are biased toward Ru over Zn.