Publication details for Dr David R.W. HodgsonCarvalho, A., O’Donoghue, A. C., Hodgson, D. R. W. & Kamerlin, S. C. L. (2015). Understanding Thio-Effects in Simple Phosphoryl Systems: Role of Solvent Effects and Nucleophile Charge. Organic and Biomolecular Chemistry 13(19): 5391-5398.
- Publication type: Journal Article
- ISSN/ISBN: 1477-0520 (print), 1477-0539 (electronic)
- DOI: 10.1039/C5OB00309A
- Further publication details on publisher web site
- Durham Research Online (DRO) - may include full text
Author(s) from Durham
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.