Synthesis and Reactivity of ortho-Carbaborane-Containing Chiral Aminohalophosphines

The synthesis of chiral ortho-carbaboranyl bis(aminohalophosphines) is presented, and spectroscopic and crystallographic data of these compounds are discussed. Furthermore, their reactivity toward alcoholysis was investigated. Quantum chemical calculations showed that the inhibition of methanolysis is of kinetic and not of thermodynamic origin. The disubstitution of the carbaboranes leads to P...P interactions as strong as a hydrogen bond that extremely lower the rate of the methanolysis.