Zn-Promoted C-H Reductive Elimination and H₂ Activation via a Dual Unsaturated Heterobimetallic Ru-Zn Intermediate

Reaction of [Ru(PPh₃)₃HCl] with LiCH₂TMS, MgMe₂, and ZnMe₂ proceeds with chloride abstraction and alkane elimination to form the bis-cyclometalated derivatives [Ru(PPh₃)(C₆H₄PPh₂)₂H][M'] where [M'] = [Li(THF)₂]⁺ (1), [MgMe(THF)₂]⁺ (3), and [ZnMe]⁺ (4), respectively. In the presence of 12-crown-4, the reaction with LiCH₂TMS yields [Ru(PPh₃)(C₆H₄PPh₂)₂H][Li(12-crown-4)₂] (2). These four complexes demonstrate increasing interaction between M' and the hydride ligand in the [Ru(PPh₃)(C₆H₄PPh₂)₂H]^- anion following the trend 2 (no interaction) < 1 < 3 < 4 both in the solid-state and solution. Zn species 4 is present as three isomers in solution including square-pyramidal [Ru(PPh₃)₂(C₆H₄PPh₂)(ZnMe)] (5), that is formed via C-H reductive elimination and features unsaturated Ru and Zn centers and an axial Z-type [ZnMe]⁺ ligand. A [ZnMe]⁺ adduct of 5, [Ru(PPh₃)₂(C₆H₄PPh₂)(ZnMe)₂][BAr^F₄] (6) can be trapped and structurally characterized. 4 reacts with H₂ at -40 °C to form [Ru(PPh₃)₃(H)₃(ZnMe)], 8-Zn, and contrasts the analogous reactions of 1, 2, and 3 that all require heating to 60 °C. This marked difference in reactivity reflects the ability of Zn to promote a rate-limiting C-H reductive elimination step, and calculations attribute this to a significant stabilization of 5 via Ru → Zn donation. 4 therefore acts as a latent source of 5 and this operational "dual unsaturation" highlights the ability of Zn to promote reductive elimination in these heterobimetallic systems. Calculations also highlight the ability of the heterobimetallic systems to stabilize developing protic character of the transferring hydrogen in the rate-limiting C-H reductive elimination transition states.