Towards Reagents for Bimetallic Activation Reactions: Polyhydride Complexes with Ru₂H₃, Ru₂ZnH₆, and Cu₂Ru₂H₆ Cores

Abstract

Abstract The utility of the fac ‐[RuH 3 (PR 3 ) 3 ] – anion (R = Ph, C 6 H 4 ‐4‐Me) for the preparation of new oligonuclear transition metal polyhydrides has been examined. The lithium salts [Li(thf) x {Ru(μ‐H) 3 (PPh 3 ) 3 }] { 1 : R = Ph, x = 3; 1′ : R = C 6 H 4 ‐4‐Me (Tol), x = 2.5} react with [Cp*RuCl] 4 (Cp* = C 5 Me 5 ), ZnCl 2 , and CuCl(SMe 2 ) to form new oligonuclear polyhydrido complexes. The compounds [Cp*Ru(μ‐H) 3 Ru(PR 3 ) 3 ] ( 2: R = Ph, 2′ : R = Tol), [Zn{Ru(μ‐H) 3 (PPh 3 ) 3 } 2 ] ( 3 ), and [Cu 2 {Ru(μ‐H) 3 (PPh 3 ) 3 } 2 ] ( 4 ) were synthesized and characterized by multinuclear NMR and IR spectroscopy, and microanalysis. The molecular structures were determined by X‐ray crystallography. Density functional theory calculations at the PBE‐D3/def2‐TZVP level support the proposed structures of the new polyhydride complexes. The impact of intramolecular London dispersion interactions on the optimized geometries is discussed.