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Ab initio and DFT studies on hydrolyses of phosphorus halides
Author(s) -
Lee OhSeuk,
Yang Kiyull,
Kang Keum Duck,
Koo In Sun,
Kim ChanKyung,
Lee Ikchoon
Publication year - 2004
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20104
Subject(s) - halide , ab initio , phosphorus , computational chemistry , chemistry , ab initio quantum chemistry methods , organic chemistry , molecule
Hydrolyses of phosphorus halides, (RO) 2 POX where R = H or Me and X = F or Cl, in the gas phase and in the reaction field have been investigated theoretically with ab initio and the density functional theory (DFT). The free energy of activation in the reaction field was also estimated using the Onsager method with a correction of entropy change and basis set superposition error (BSSE). The reaction of (MeO) 2 POF proceeds through a path with bifunctional catalysis regardless of the medium, but the reaction of (MeO) 2 POCl proceeds through bifunctional and general base catalysis in the gas phase and in water, respectively. The estimated free energy barrier of 23 kcal/mol for the hydrolysis of (MeO) 2 POF is in good agreement with the experimental values of 24 kcal/mol, and relative barrier of 3 kcal/mol to the (MeO) 2 POCl is also in good agreement with the experimental values of 5 kcal/mol of di iso propyl phosphorus halides ((Pr i O) 2 POX, X = F and Cl). © 2004 Wiley Periodicals, Inc. J Comput Chem 25: 1740–1748, 2004