Understanding thio-effects in simple phosphoryl systems : role of solvent effects and nucleophile charge
Carvalho, Alexandra T P ; O'Donoghue, AnnMarie C ; Hodgson, David R W and Kamerlin, Shina C L LU
(2015)
In Organic and Biomolecular Chemistry
13(19).
p.8-5391
- 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.
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/e9ec2137-c71f-4e2b-9cfd-1810a936007f
- author
- Carvalho, Alexandra T P
; O'Donoghue, AnnMarie C
; Hodgson, David R W
and Kamerlin, Shina C L
LU
- publishing date
- 2015-05-21
- type
- Contribution to journal
- publication status
- published
- keywords
- Electrons, Hydrogen-Ion Concentration, Hydrolysis, Hydroxides/chemistry, Kinetics, Molecular Conformation, Organothiophosphates/chemistry, Solvents/chemistry, Water/chemistry
- in
- Organic and Biomolecular Chemistry
- volume
- 13
- issue
- 19
- pages
- 8 pages
- publisher
- Royal Society of Chemistry
- external identifiers
-
- pmid:25797408
- scopus:84929094583
- ISSN
- 1477-0539
- DOI
- 10.1039/c5ob00309a
- language
- English
- LU publication?
- no
- id
- e9ec2137-c71f-4e2b-9cfd-1810a936007f
- date added to LUP
- 2025-01-11 21:37:08
- date last changed
- 2025-01-22 03:23:51
@article{e9ec2137-c71f-4e2b-9cfd-1810a936007f,
abstract = {{<p>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.</p>}},
author = {{Carvalho, Alexandra T P and O'Donoghue, AnnMarie C and Hodgson, David R W and Kamerlin, Shina C L}},
issn = {{1477-0539}},
keywords = {{Electrons; Hydrogen-Ion Concentration; Hydrolysis; Hydroxides/chemistry; Kinetics; Molecular Conformation; Organothiophosphates/chemistry; Solvents/chemistry; Water/chemistry}},
language = {{eng}},
month = {{05}},
number = {{19}},
pages = {{8--5391}},
publisher = {{Royal Society of Chemistry}},
series = {{Organic and Biomolecular Chemistry}},
title = {{Understanding thio-effects in simple phosphoryl systems : role of solvent effects and nucleophile charge}},
url = {{http://dx.doi.org/10.1039/c5ob00309a}},
doi = {{10.1039/c5ob00309a}},
volume = {{13}},
year = {{2015}},
}