Understanding Thio-Effects in Simple Phosphoryl Systems: Role of Solvent Effects and Nucleophile Charge

Carvalho, A.; O’Donoghue, A.C.; Hodgson, D.R.W.; Kamerlin, S.C.L.

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.

Citation

Carvalho, A., O’Donoghue, A., Hodgson, D., & Kamerlin, S. (2015). Understanding Thio-Effects in Simple Phosphoryl Systems: Role of Solvent Effects and Nucleophile Charge. Organic and Biomolecular Chemistry, 13(19), 5391-5398. https://doi.org/10.1039/c5ob00309a

• Journal Article Type: Article
• Acceptance Date: Feb 25, 2015
• Publication Date: May 21, 2015
• Deposit Date: Apr 8, 2015
• Publicly Available Date: Apr 28, 2015
• Journal: Organic and Biomolecular Chemistry
• Print ISSN: 1477-0520
• Electronic ISSN: 1477-0539
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 13
• Issue: 19
• Pages: 5391-5398
• DOI: https://doi.org/10.1039/c5ob00309a
• Public URL: https://durham-repository.worktribe.com/output/1443385