Understanding thio-effects in simple phosphoryl systems: role of solvent effects and nucleophile charge
2015 (English)In: Organic and biomolecular chemistry, ISSN 1477-0520, E-ISSN 1477-0539, Vol. 13, no 19, 5391-5398 p.Article in journal (Refereed) Published
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 S(N)2(P) mechanisms as the basis of these differences, rather than a change in mechanism.
Place, publisher, year, edition, pages
2015. Vol. 13, no 19, 5391-5398 p.
IdentifiersURN: urn:nbn:se:uu:diva-256560DOI: 10.1039/c5ob00309aISI: 000354205600012PubMedID: 25797408OAI: oai:DiVA.org:uu-256560DiVA: diva2:825880
FunderSwedish National Infrastructure for Computing (SNIC), 25/2-10