Ruthenium Diphosphine Closo-C2B9-Carborane Clusters with Nitrile Ligands: Synthesis and Structure Determination

Abstract

The interaction of 3,3-(Ph2P(CH2)4PPh2)-3-H-3-Cl-closo-3,1,2-RuC2B9H11 (1) with isopropylamine and corresponding nitrile (NCR) in dichloromethane at 40\xa0°C yields carborane clusters of Ru(II) with nitrile ligand [3,3-(Ph2P(CH2)4PPh2)-3-NCR-closo-3,1,2-RuC2B9H11] (R\u2009=\u2009 –Ph, –CH=CH2). A similar ortho-cycloboronated clusters [3-NCR-3,3,8-{(Ph2P(CH2)4PPh-μ-(C6H4-ortho)}closo-3,1,2-RuC2B9H10] were obtained from the corresponding chlorine-containing ruthenacarboranes. The novel clusters were isolated as yellow crystal solids and characterized by NMR, mass-spectroscopy and X-ray analysis. The reaction of the obtained clusters with HCl showed the chemical reversibility of dehydrohalogenation. The performed electrochemical investigation testified the ability of novel complexes to undergo reversible oxidation to Ru(III) species.