Novel Group 4 metal–ruthenium complexes. Synthesis, structure and reactivity of the first thiolato-bridged titanium–ruthenium and zirconium–ruthenium complexes

Abstract

Complexes [TiCp₂(SR)₂] (R = Ph or Me) reacted with [RuCl(Cp*)(cod)] (cod = cycloocta-1,5-diene) to afford [Cp₂Ti(µ-SR)₂RuCl(Cp*)] (Cp = cyclopentadienyl, Cp* = pentamethylcyclopentadienyl; R = Ph 1a or Me 1b). X-Ray analysis of 1a showed that two phenyl groups on the sulfur atoms are in syn conformation. The complex [Cp₂Zr(µ-SMe)₂RuCl(Cp*)] 1d was also prepared. Complexes 1a and 1b reacted with KBH(Bu^s)₃ to afford hydrido complexes [Cp₂Ti(µ-SR)₂RuH(Cp*)] (R = Ph 2a or Me 2b), and with Ag⁺ in the presence of ligands to afford [Cp₂Ti(µ-SR)₂Ru(L)Cp*]⁺X^– (R = Ph, L = CO, X = BF₄ 3a; R = Me, L = CO, X = PF₆ 3b; R = Ph, L = Bu^tNC, X = BF₄ 4a; R = Me, L = Bu^tNC, X = PF₆ 4b; R = Ph, L = Bu^tCN, X = PF₆ 5a; R = Me, L = Bu^tCN, X = PF₆ 5b; R = Ph, L = MeCN, X = PF₆ 6a; R = Me, L = MeCN, X = PF₆ 6b). The structures of these cationic complexes were also revealed by X-ray analysis.