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Photo Lynn Kamerlin

Lynn Kamerlin

Professor

Photo Lynn Kamerlin

Understanding thio-effects in simple phosphoryl systems : role of solvent effects and nucleophile charge

Author

  • Alexandra T P Carvalho
  • AnnMarie C O'Donoghue
  • David R W Hodgson
  • Shina C L Kamerlin

Summary, in English

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.

Publishing year

2015-05-21

Language

English

Pages

8-5391

Publication/Series

Organic and Biomolecular Chemistry

Volume

13

Issue

19

Document type

Journal article

Publisher

Royal Society of Chemistry

Keywords

  • Electrons
  • Hydrogen-Ion Concentration
  • Hydrolysis
  • Hydroxides/chemistry
  • Kinetics
  • Molecular Conformation
  • Organothiophosphates/chemistry
  • Solvents/chemistry
  • Water/chemistry

Status

Published

ISBN/ISSN/Other

  • ISSN: 1477-0539