Pentamethylcyclopentadienyl ruthenium(III) vs hexamethylbenzene ruthenium(II) in sulfur-centered reactivity of their thioether-thiolate and allied complexes

The reactivity features of [Cp*Ru(III){eta(3)-tpdt)}] (7) and [(HMB)Ru(II)(eta(3)-tpdt)] (10) {Cp* = eta(5)-C(5)Me(5); HMB = eta(6)-C(6)Me(6); tpdt = 3-thiapentane-1,5-dithiolate, S(CH(2)CH(2)S(-))(2)} are presented, together with selected aspects of their (eta(3)-apdt) analogues 8 and 11 {apdt = 3-azapentane-1,5-dithiolate, HN(CH(2)CH(2)S(-))(2)}. This account will highlight the differences observed in their reactions with metal fragments of compounds of Ru and groups 10 and 11 in various coordination environments and with alkylating agents, including alpha,omega-dibromoalkanes. The mechanistic pathway of the alkylation of 7 will be discussed in some detail.