Studies on arene ruthenium thiolate and related complexes

Abstract

New hexamethylbenzene and pentamethylcyclopentadienyl complexes of ruthenium, viz. [(HMB)Ru(I?3-tpdt)] (1), [(HMB)Ru{I?3-NS2}] (2), [Cp*Ru{I?3-tpdt)}] (3), and [Cp*Ru{I?3-NS2}] (4) {HMB = I?6-C6Me6; Cp* = I?5-C5Me5; tpdt = 3-thiapentane-1,5-dithiolate; NS2 = 3-azapentane-1,5-dithiolate} have been synthesized. Hetero di-, tri-, and tetra-nuclear complexes have been obtained from the reactions of 1 and 3 towards [Cp*RuCl2]2, and compounds of groups 10, 11 and 14. Complexes 1-3 were also reacted with alkylating reagents, I?,I?-dibromoalkanes, Br(CH2)nBr (where n = 2-4), and bromoalkenes, CH2=CH(CH2)nBr (n = 1, 2). A detailed study of the mechanism of the reaction of 3 revealed an unusual example of reversible homolytic sulfur-sulfur bond formation. The electrochemistry and electron spin resonance (EPR) studies of some of the new products have been carried out.