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Intramolecular Communication in Anionic Oxidized Phosphanes through a Chelated Proton
Author(s) -
Popescu A. R.,
Rojo I.,
Teixidor F.,
Sillanpää R.,
Viñas C.
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201500307
Subject(s) - natural bond orbital , intramolecular force , chemistry , cluster (spacecraft) , hydrogen peroxide , chelation , phosphorus , proton , carborane , hydrogen bond , photochemistry , inorganic chemistry , computational chemistry , medicinal chemistry , molecule , density functional theory , stereochemistry , organic chemistry , physics , quantum mechanics , computer science , programming language
Oxidation of the 1,2‐(PR 2 ) 2 ‐1,2‐ closo‐ C 2 B 10 H 10 (R=Ph, i Pr) 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.