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

Complexes [TiCp2(SR)(2)] (R = Ph or Me) reacted with [RuCl(Cp*)(cod)] (cod = cycloocta-1,5-diene) to afford [Cp2Ti(mu-SR)(2)RuCl(Cp*)] (Cp = cyclopentadienyl, Cp* = pentamethylcyclopentadienyl; R = Ph la or Me Ib). X-Ray analysis of la showed that two phenyl groups on the sulfur atoms are in syn conformation. The complex [Cp2Zr(mu-SMe)(2)RuCl(Cp*)] 1d was also prepared. Complexes la and Ib reacted with KBH(Bu-S)(3) to afford hydride complexes [Cp2Ti(mu-SR)(2)RuH(Cp*)] (R = Ph 2a or Me 2b), and with Ag+ in the presence of ligands to afford [Cp2Ti(mu-SR)(2)Ru(L)Cp*]X-+(-) (R = Ph, L = CO, X = BF4 3a; R = Me, L = CO, X = PF6 3b; R = Ph, L = (BuNC)-N-t, X = BF4 4a; R = Me, L = (BuNC)-N-t, X = PF6 4b; R = Ph, L = (BuCN)-C-t, X = PF6 5a; R = Me, L = (BuCN)-C-t, 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.