Abstract
Cp*Ru Thiol Complexes, II[1]. – Adduct Formation in [Cp*RuII(μ‐SR)]2 and Cp*Ru(C6F5)(μ‐SC6F5)(μ‐S)RuCp*]. Molecular Structure of cis‐[Cp*Ru(μ2‐StBu)(CO)]2 and [Cp*Ru(C6F5)(μ‐SC6F5)(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). C6F5SH as thiol reacts with 1 to form [Cp*Ru(C6F5)(μ‐SC6F5)(μ‐S)RuCp*] (3a) with oxidative migration of a C6F5 group from S to Ru. For elucidation of the constitutions molecular structures of 3a and cis‐[Cp*Ru(μ‐StBu)(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 C6F5SH yield complexes [{Cp*Ru(μ‐SR)}2(dppm)] (R = Ph 5, C6F5 6).
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