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

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...

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Detalles Bibliográficos
Autores principales: Carvalho, Alexandra T. P., O'Donoghue, AnnMarie C., Hodgson, David R. W., Kamerlin, Shina C. L.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2015
Materias:
Chemistry
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4425225/
https://www.ncbi.nlm.nih.gov/pubmed/25797408
http://dx.doi.org/10.1039/c5ob00309a
Descripción
Sumario: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.

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