(Indenyl)ruthenium Complexes Containing 1,1'-Bis(diphenylphosphanyl)-ferrocene(dppf)and Thiolato Ligands:Synthesis,X-ray Structure Analysis,Electrochemistry and Magnetic Studies

摘要

The reaction of [(Ind)Ru(dppf)Cl](Ind = eta~5-C_9H_7)(2)with RSNa {R = Me,Et,Ph,Ph_2P(CH_2)_2} proceeds in MeOH to give [(Ind)Ru(dppf)(SR)] {R = Me(3),Et(4),Ph(5),Ph_2P(CH_2)_2(7)),as well as [(Ind)Ru(dppf)H](6),in all cases except for R = Ph.This R-dependence of the product mixture was rationalised on a RS"/MeOH <-> MeCr/RSH equilibrium involving the interaction of thiolate(RS~-)with MeOH,and the relative nu-cleophilicities of RS~- versus MeCn 6 arose from beta-H elimi-nation from an OMe derivative.Cyclic voltammetric measurements on 2,3,4 and 5,as well as the Cp(eta~5-C_5H_5)and Cp*(eta~5-C_5Me_5)analogues of 2,indicated that the formal oxidation potentials for [LRu(dppf)Cl] complexes {L = Ind(2),Cp(2A)and Cp*(2B)} occurred in the order Cp* < Ind < Cp,correlating with the more electron-donating groups lowering the oxidation potentials.EPR experiments performed on the one-electron oxidised forms of 3 and 5 indicated paramagnetic compounds with g values close to 2,while the two-electron oxidised forms of 3 and 5 were diamagnetic.All the complexes were characterised spectroscopically,and 5 and 6 also crystallographically.