C*Ru‐Thiolkomplexe, II [1] . Adduktbildung in [Cp*Ru II (π‐SR)] 2 und [Cp*Ru(C 6 F 5 )(μ‐SC 6 F 5 )(μ‐S)RuCp*]. Molekülstruktur von cis ‐[Cp*Ru(μ 2 ‐S t Bu)(CO)] 2 und [Cp*Ru(C 6 F 5 )(μ‐SC 6 F 5 )(μ‐S)RuCp*]

Cp*Ru Thiol Complexes, II [1] . – Adduct Formation in [Cp*Ru II (μ‐SR)] 2 and Cp*Ru(C 6 F 5 )(μ‐SC 6 F 5 )(μ‐S)RuCp*]. Molecular Structure of cis ‐[Cp*Ru(μ 2 ‐S t Bu)(CO)] 2 and [Cp*Ru(C 6 F 5 )(μ‐SC 6 F 5 )(μ‐S)RuCp*] Reaction of [Cp*Ru(μ‐OMe)] 2 ( 1 ) with thiols RSH gave the sulfur analogues to 1 , [Cp*Ru(μ‐SR)] 2 ( 2 ), and with PhSH after carbonylation cis ‐[Cp*Ru(μ‐SPh)(CO)] 2 ( 11 ). C 6 F 5 SH as thiol reacts with 1 to form [Cp*Ru(C 6 F 5 )(μ‐SC 6 F 5 )(μ‐S)RuCp*] ( 3a ) with oxidative migration of a C 6 F 5 group from S to Ru. For elucidation of the constitutions molecular structures of 3a and cis ‐[Cp*Ru(μ‐S t Bu)(CO)] ( 10 ) were determined by single crystal X‐ray diffraction. Adduct formation and bridge cleavage of the doubly coordinatively unsaturated dinuclear complexes 2 and singly unsaturated complex 3 with donor and acceptor ligands is investigated and the donor/acceptor character of the Ru centers in thiol complexes 2 compared to those in 1 . Substitution reactions of [{Cp*Ru(μ‐OMe)} 2 (dppm)] ( 4 ) with PhSH and C 6 F 5 SH yield complexes [{Cp*Ru(μ‐SR)} 2 (dppm)] (R = Ph 5 , C 6 F 5 6 ).