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Intramolecular Communication in Anionic Oxidized Phosphanes through a Chelated Proton
Authors:Dr A R Popescu  Dr I Rojo  Prof Dr F Teixidor  Prof Dr R Sillanpää  Prof Dr C Viñas
Institution:1. Institut de Ciència de Materials de Barcelona, Campus U.A.B., 08193 Bellaterra (Spain), Fax: (+34)?93‐580‐57‐29;2. Department of Chemistry, University of Jyv?skyl?, 40014, Jyv?skyl? (Finland)
Abstract: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.
Keywords:carboranes  carboranylphosphanes  hydrogen bonds  oxidation  phosphorus
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