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(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(Bus)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 = ButNC, X = BF4 4a; R = Me, L = ButNC, X = PF6 4b; R = Ph, L = ButCN, X = PF6 5a; R = Me, L = ButCN, 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.