Introduction of a Methoxy Group into a Hydrocarbyl Ligand Derived from a Linear Alkane on a Triruthenium Cluster via Chemical Oxidation

The two-electron oxidation of a closo-ruthenacyclopentadiene complex, [(Cp*Ru)2{Cp*Ru(μ3-CMeCHCHCH−)}(μ-H)] (2a), derived from the reaction of a triruthenium complex, {Cp*Ru(μ-H)}3(μ3-H)2 (1), with n-pentane, resulted in the formation of a dicationic complex, [{Cp*Ru(μ-H)}2{Cp*Ru(μ3-C(CH2)CHCHCH−)}]2+ (7), having an exo methylene group on the metallacycle moiety. The treatment of 7 with methanol resulted in the nucleophilic addition of a methoxy group to form a cationic closo-ruthenacyclopentadiene complex, [{Cp*Ru(μ-H)}2{Cp*Ru(μ3-C(CH2OMe)CHCHCH−)}]+ (9a), demonstrating the functionalization of a hydrocarbyl ligand originating from n-pentane.