Rhodacarboranes containing σ- and π-carborane ligands. New aspects

Abstract Number of novel charge-compensated rhodacarboranes with pyridinium group was synthesized and characterized. Synthesis of 16-electron 3,3-μ-(1′,2′-C2B10H10-1′,2′-S2-)-4-Py-3,1,2-RhC2B9H10 was accompanying by formation of several products. They were isolated and identified as two diastereomers of unusual dirhodacarboranes which contain two π-carboranyl and one σ-dithiolate ligands 3,3-μ3-(1′,2′-C2B10H10-1′,2′-S2-)-(4-Py-3,1,2-RhC2B9H10)2. Structure of the DD/LL-isomer was determined by single crystal X-ray diffraction. Reaction the 16-electron complex with trimethylphosphine leads to corresponding 18-electron complex 3-PMe3-3,3-μ-(1′,2′-C2B10H10-1′,2′-S2-)-4-Py-3,1,2-RhC2B9H10. Its structure was also confirmed by single crystal X-ray diffraction.