Reactions of 5,6,10-{Cl(Ph3P)2Ru}-[5,6,10-(μ-H)3-10-H-exo-nido-7,8-C2B9H8] with bis(diphenylphosphino)methane and 1,2-bis(diphenylphosphino)benzene: specific features

Specific features of reactions of complex 5,6,10-{Cl(Ph3P)(2)Ru}-[5,6,10-(mu-H)(3)-10-H-exo-nido-7,8-C2B9H8] (1) with 1,2-bis(diphenylphosphino)benzene (dppbz) and bis(diphenylphosphino)methane (dppm) in acetonitrile in the presence of amines were studied. Novel closo-ruthenacarborane complexes containing the metal in a formal oxidation state of +2 were isolated. It was established that the reaction of 1 with dppbz affords a complex containing a coordinated acetonitrile molecule, whereas the reaction with dppm results in a tris(phosphine) complex with strongly sterically shielded ruthenium center. Reactions of the newly obtained compounds with carbon tetrachloride or hydrogen chloride give corresponding 17-electron complexes containing the metal atom in a formal oxidation state of +3. The reversibility of the Ru-II -> Ru-III redox transition in the compounds synthesized was investigated by cyclic voltammetry and the influence of the ligand environment on the values of the corresponding redox potentials was assessed.

Automated summary

The reactions of complex 5,6,10-{Cl(Ph3P)(2)Ru}-[5,6,10-(mu-H)(3)-10-H-exo-nido-7,8-C2B9H8] (1) with 1,2-bis(diphenylphosphino)benzene (dppbz) and bis(diphenylphosphino)methane (dppm) in the presence of amines were investigated. New closo-ruthenacarborane complexes with a formal oxidation state of +2 were synthesized. The reaction with dppbz led to the formation of a complex containing a coordinated acetonitrile molecule, while the reaction with dppm resulted in a tris(phosphine) complex with a sterically shielded ruthenium center. The reversibility of the Ru-II -> Ru-III redox transition in these compounds was studied using cyclic voltammetry and the effect of the ligand environment on the redox potentials was evaluated.