✦ LIBER ✦
Ab initio calculations on P—C bond cleavage in phosphoranyl radicals: implications for the biodegradation of organophosphonate derivatives
✍ Scribed by Myong Lim; Christopher J. Cramer
- Publisher
- John Wiley and Sons
- Year
- 1998
- Tongue
- English
- Weight
- 156 KB
- Volume
- 11
- Category
- Article
- ISSN
- 0894-3230
No coin nor oath required. For personal study only.
✦ Synopsis
Barrier heights for P-C bond homolysis in P-hydroxy-P-methyl-P,P-dioxophosphoranyl and P,P,Ptrihydroxy-P-methylphosphoranyl were calculated using well correlated levels of electronic structure theory. The best estimate for the difference in barriers between the two indicates that homolysis is more facile for P,P,P-trihydroxy-Pmethylphosphoranyl by roughly 9 kcal mol À1 . This result suggests that bacterial pathways leading to P-C bond cleavage in organophosphonate derivatives will preferentially proceed via initial one-electron reduction of substrates rather than oxidation.