title: Activating water: important effects of non-leaving groups on the hydrolysis of phosphate triesters.
abstract: The high rate of spontaneous hydrolysis of tris-2-pyridyl phosphate (TPP) is explained by the activating effects of the non-leaving ("spectator") groups on P-OAr cleavage, and not by intramolecular catalysis. Previous work on phosphate-transfer reactions has concentrated on the contributions to reactivity of the nucleophile and the leaving group, but our results make clear that the effects of the non-leaving groups on phosphorus can be equally significant. Rate measurements for three series of phosphate triesters showed that sensitivities to the non-leaving groups are substantial for spontaneous hydrolysis reactions, although significantly smaller for reactions with good nucleophiles. There are clear differences between triaryl and dialkyl aryl triesters in sensitivities to leaving and non-leaving groups with the more reactive triaryl systems showing lower values for both β(LG) and β(NLG). Intramolecular catalysis of the hydrolysis of TPP by the neighbouring pyridine nitrogens is insignificant, primarily because of their low basicity.
authors: University Chemical Laboratory, Cambridge, CB2 1EW, UK. ajk1@cam.ac.uk
authors: Anthony J
authors: AJ
authors: Kirby
authors: Michelle
authors: M
authors: Medeiros
authors: Pedro S M
authors: PS
authors: Oliveira
authors: Elisa S
authors: ES
authors: Orth
authors: Tiago A S
authors: TA
authors: Brandão
authors: Eduardo H
authors: EH
authors: Wanderlind
authors: Almahdi
authors: A
authors: Amer
authors: Nicholas H
authors: NH
authors: Williams
authors: Faruk
authors: F
authors: Nome
mesh_terms: D002384:Catalysis; D006863:Hydrogen-Ion Concentration; D006868:Hydrolysis; D007700:Kinetics; D015394:Molecular Structure; D010755:Organophosphates / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*
chemical_list: D010755:Organophosphates; D011725:Pyridines