Bonding and Reactivity of a Pair of Neutral and Cationic Heterobimetallic RuZn(2) Complexes

[Image: see text] A combined experimental and computational study of the structure and reactivity of two [RuZn(2)Me(2)] complexes, neutral [Ru(PPh(3))(Ph(2)PC(6)H(4))(2)(ZnMe)(2)] (2) and cationic [Ru(PPh(3))(2)(Ph(2)PC(6)H(4))(ZnMe)(2)][BAr(F)(4)] ([BAr(F)(4)] = [B{3,5-(CF(3))(2)C(6)H(3)}(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···C(aryl) interaction with a cyclometalated phosphine ligand, this being stronger in 3. Both 2 and 3 show diverse reactivity under thermolysis and with Lewis bases (P(n)Bu(3), PCy(3), and IMes). With 3, all three Lewis bases result in the loss of [ZnMe](+). In contrast, 2 undergoes PPh(3) substitution with P(n)Bu(3), but with IMes, loss of ZnMe(2) occurs to form [Ru(PPh(3))(C(6)H(4)PPh(2))(C(6)H(4)PPhC(6)H(4)Zn(IMes))H] (7). The reaction of 3 with H(2) affords the cationic trihydride complex [Ru(PPh(3))(2)(ZnMe)(2)(H)(3)][BAr(F)(4)] (12). Computational analyses indicate that both 12 and 7 feature bridging hydrides that are biased toward Ru over Zn.