SYNTHESIS AND ELECTROCHEMISTRY OF ORGANOMETALLIC ETHANETHIOLATO BRIDGED COMPLEXES OF RUTHENIUM(IV)

Reaction of the ruthenium(IV) chloro-bridged dimer [{RU(eta(3):eta(3)-C10H16)Cl(mu-Cl)}(2)], 1, with ethanethiol (EtSH) in CH2Cl2 gives the bridged-cleaved adduct [Ru(eta(3):eta(3)-C10H16)Cl-2(SHEt)], 2. Stirring of two molar equivalents of 2 in methanol with one equivalent of 1 gives the binuclear, mixed chloro/thiolato bridged compound [{RU(eta(3):eta(3)- C10H16)Cl}(2)(mu-Cl)(mu-SEt)], 3. The related doubly thiolato bridged complex [{Ru(eta 3:eta 3-C10H16)Cl(mu-SEt)}(2)], 4, is formed by treatment of 1 with an excess of EtSH, or by prolonged stirring of 2 alone in methanol. Compounds 2-4 have been studied by cyclic voltammetry. Compound 2 undergoes only irreversible oxidation, whereas in the case of both 3 and 4 the observation of significant return waves is consistent with a greater stability of the primary redox products.