Ab Initio Calculations on P-C Bond Cleavage in Phosphoranyl Radicals: Implications for the Biodegradation of Organophosphonate Derivatives

Lim, M.; Cramer, C. J.
J. Phys. Org. Chem. 1998, 11, 149.

Barrier heights for P-C bond homolysis in P-hydroxy-P-methyl-P,P-dioxophosphoranyl and P,P,P-trihydroxy-P-methylphosphoranyl have been calculated using well correlated levels of electronic structure theory. Our best estimate for the difference in barriers between the two indicates that homolysis is more facile for P,P,P-trihydroxy-P-methylphosphoranyl by roughly 9 kcal/mol. This result suggests that bacterial pathways leading to P-C bond cleavage in organophosphonate derivatives will preferentially proceed via initial 1-electron reduction of substrates rather than oxidation.

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