The Competing Mechanisms of Phosphate Monoester Dianion Hydrolysis.

ABSTRACT: Despite the numerous experimental and theoretical studies on phosphate monoester hydrolysis, significant questions remain concerning the mechanistic details of these biologically critical reactions. In the present work we construct a linear free energy relationship for phosphate monoester hydrolysis to explore the effect of modulating leaving group pKa on the competition between solvent- and substrate-assisted pathways for the hydrolysis of these compounds. Through detailed comparative electronic-structure studies of methyl phosphate and a series of substituted aryl phosphate monoesters, we demonstrate that the preferred mechanism is dependent on the nature of the leaving group. For good leaving groups, a strong preference is observed for a more dissociative solvent-assisted pathway. Howev

SUBMITTER: Duarte F 

PROVIDER: S-EPMC4999962 | biostudies-literature | 2016 Aug

REPOSITORIES: biostudies-literature