title: Understanding thio-effects in simple phosphoryl systems: role of solvent effects and nucleophile charge.
abstract: Recent experimental work (J. Org. Chem., 2012, 77, 5829) demonstrated pronounced differences in measured thio-effects for the hydrolysis of (thio)phosphodichloridates by water and hydroxide nucleophiles. In the present work, we have performed detailed quantum chemical calculations of these reactions, with the aim of rationalizing the molecular bases for this discrimination. The calculations highlight the interplay between nucleophile charge and transition state solvation in SN2(P) mechanisms as the basis of these differences, rather than a change in mechanism.
authors: Science for Life Laboratory, Department of Cell and Molecular Biology, Uppsala University, BMC Box 596, SE-751 24, Uppsala, Sweden. kamerlin@icm.uu.se.
authors: Alexandra T P
authors: AT
authors: Carvalho
authors: AnnMarie C
authors: AC
authors: O'Donoghue
authors: David R W
authors: DR
authors: Hodgson
authors: Shina C L
authors: SC
authors: Kamerlin
mesh_terms: D004583:Electrons; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D006878:Hydroxides / Q000737:chemistry; D007700:Kinetics; D008968:Molecular Conformation; D063086:Organothiophosphates / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D006878:Hydroxides; D063086:Organothiophosphates; D012997:Solvents; D014867:Water; C031356:hydroxide ion