期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 17, 期 52, 页码 14996-15004出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201101926
关键词
basicity; hydrolysis; intramolecular catalysis; kinetics; phosphorus
资金
- FAPESC (Fundaco de Apoio a Pesquisa Cientifica e Tecnologica do Estado de Santa Catarina)
- CNPq (Conselho Nacional de Desenvolvimento Cientifico e Tecnologico)
- INCT-Catalise (Instituto Nacional de Ciencia e Tecnologia
- Brazil)
- EPSRC (Engineering and Physical Sciences Research Council, UK) [EP/E01917X]
- Libyan Ministry of Higher Education
- Engineering and Physical Sciences Research Council [EP/E01917X/1] Funding Source: researchfish
- EPSRC [EP/E01917X/1] Funding Source: UKRI
The high rate of spontaneous hydrolysis of tris-2-pyridyl phosphate (TPP) is explained by the activating effects of the non-leaving (spectator) groups on P-OAr cleavage, and not by intramolecular catalysis. Previous work on phosphate-transfer reactions has concentrated on the contributions to reactivity of the nucleophile and the leaving group, but our results make clear that the effects of the non-leaving groups on phosphorus can be equally significant. Rate measurements for three series of phosphate triesters showed that sensitivities to the non-leaving groups are substantial for spontaneous hydrolysis reactions, although significantly smaller for reactions with good nucleophiles. There are clear differences between triaryl and dialkyl aryl triesters in sensitivities to leaving and non-leaving groups with the more reactive triaryl systems showing lower values for both beta LG and beta NLG. Intramolecular catalysis of the hydrolysis of TPP by the neighbouring pyridine nitrogens is insignificant, primarily because of their low basicity.
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