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Ab initio and DFT studies on hydrolyses of phosphorus halides

✍ Scribed by Oh-Seuk Lee; Kiyull Yang; Keum Duck Kang; In Sun Koo; Chan-Kyung Kim; Ikchoon Lee

Publisher
John Wiley and Sons
Year
2004
Tongue
English
Weight
775 KB
Volume
25
Category
Article
ISSN
0192-8651

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✦ Synopsis

Abstract

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). Β© 2004 Wiley Periodicals, Inc. J Comput Chem 25: 1740–1748, 2004

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