CP(ASTERISK)RU THIOL COMPLEXES .2. ADDUCT FORMATION IN [CP(ASTERISK)RU(II)(MU-SR)](2) AND P(ASTERISK)-RU(C6F5)(MU-SC6F5)(U-S)RUCP(ASTERISK)] - MOLECULAR-STRUCTURE OF CIS-[CP(ASTERISK)RU(MU(2)-STBU)(CO)](2)] AND [ P(ASTERISK)RU(C6F5)(MU-SC6F5)(MU-S)RUCP(ASTERISK)]

Reaction of [CpRu(mu-OMe)](2) (1) with thiols RSH gave the sulfur ana logues to 1, [CpRu(mu-SR)](2) (2), and with PhSH after carbonylation cis-[CpRu(mu-SPh)(CO)](2), (11). C6F5SH as thiol reacts with 1 to for m [CpRu(C6F5)(mu-SC6F5)(mu-S)RuCp*] (3a) with oxidative migration of a C6F5 group from S to Ru. For elucidation of the constitutions molecu lar structures of 3a and cis-[CpRu(mu-StBu)(C0)] (10) were determined by single crystal X-ray diffraction. Adduct formation and bridge clea vage of the doubly coordinatively unsaturated dinuclear complexes 2 an d singly unsaturated complex 3 with donor and acceptor ligands is inve stigated and the donor/acceptor character of the Ru centers in thiol c omplexes 2 compared to those in 1. Substitution reactions of [{CpRu(m u-OMe)}(2)(dppm)] (4) with PhSH and C6F5SH yield complexes [{CpRu(mu- SR)}(2)(dppm)] (R = Ph 5, C(6)F(5)6).