Intramolecular Communication in Anionic Oxidized Phosphanes through a Chelated Proton

Oxidation of the 1,2‐(PR2)2‐1,2‐closo‐C2B10H10 (R=Ph, iPr) platform with hydrogen peroxide in acetone is a two‐step procedure in which partial deboronation of the closo cluster and oxidation of the phosphorus atoms occur. Based on NMR spectroscopic and kinetic data, we demonstrate that the phosphorus atoms are oxidized in the first step, followed by cluster deboronation. DFT calculations and natural‐bond orbital (NBO) analysis were used to obtain insight into the electronic structures of diphosphane ortho‐carborane derivatives. A good influence: Kinetic and computational studies on the oxidation of carboranylphosphanes help interpret the rare intramolecular electronic communication present in these compounds. The carborane influence on the directly connected phosphorus atom is demonstrated. The oxidation of carboranyldiphosphane with hydrogen peroxide in acetone is a two‐step procedure, in which the phosphorus atoms are oxidized first, followed by cluster deboronation (see figure).