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

Journal of the American Chemical Society
Fedor M MiloserdovMichael K Whittlesey

Abstract

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][BArF4] (6) can be trapped and structurally characterized. 4 reacts with H2 at -40oC 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 60oC. 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 si...Continue Reading

References

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Citations

Jun 17, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Tharun Teja PonduruH V Rasika Dias
Jul 30, 2020·Chemistry : a European Journal·Sonia BajoJesus Campos
Jan 5, 2021·Chemical Communications : Chem Comm·Shin TakemotoHiroyuki Matsuzaka
Nov 16, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Siyuan L XieMichael D Fryzuk

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