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

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

SUBMITTER: Miloserdov FM 

PROVIDER: S-EPMC7660749 | biostudies-literature | 2020 Apr

REPOSITORIES: biostudies-literature