Phosphorane lifetime and stereo-electronic effects along the alkaline hydrolysis of phosphate esters

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dc.creatorEufrásia de Sousa Pereira
dc.creatorJulio Cosme Santos da Silva
dc.creatorTiago Antônio da Silva Brandão
dc.creatorWillian Ricardo Rocha
dc.date.accessioned2023-09-29T11:44:55Z
dc.date.accessioned2025-09-08T23:50:27Z
dc.date.available2023-09-29T11:44:55Z
dc.date.issued2016
dc.description.sponsorshipCNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológico
dc.description.sponsorshipFAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Gerais
dc.description.sponsorshipINCT – Instituto nacional de ciência e tecnologia (Antigo Instituto do Milênio)
dc.identifier.doihttps://doi.org/10.1039/C6CP01536K
dc.identifier.issn1463-9084
dc.identifier.urihttps://hdl.handle.net/1843/59023
dc.languageeng
dc.publisherUniversidade Federal de Minas Gerais
dc.relation.ispartofPhysical Chemistry Chemical Physics
dc.rightsAcesso Restrito
dc.subjectCompostos organofosforados
dc.subjectHidrólise
dc.subjectEstereoquímica
dc.subjectMecanismos de reação (química)
dc.subjectQuímica quântica
dc.subjectFisico-quimica orgânica
dc.subjectQuímica orgânica
dc.subject.otherPhosphorane lifetime
dc.subject.otherStereo-electronic effects
dc.subject.otherPhosphate diester
dc.subject.otherPhosphate monoester
dc.subject.otherAlkaline hydrolysis
dc.subject.otherHybrid quantum mechanical / effective fragment potential (QM/EFP)
dc.subject.otherQuantum theory of atoms in molecules (QTAIM)
dc.subject.otherEnergy decomposition analysis (EDA)
dc.titlePhosphorane lifetime and stereo-electronic effects along the alkaline hydrolysis of phosphate esters
dc.typeArtigo de periódico
local.citation.epage18267
local.citation.issue27
local.citation.spage18255
local.citation.volume18
local.description.resumoHybrid quantum mechanical/effective fragment potential (QM/EFP) calculations, in conjunction with the quantum theory of atoms in molecules (QTAIM) and energy decomposition analysis (EDA), were employed to investigate the reaction mechanism and stereo-electronic effects along the alkaline hydrolysis of the monoethyl phosphate dianion (MEP) and the diethylphosphate monoanion (DEP). Reactions proceed through a synchronous bimolecular ANDN mechanism for MEP and a stepwise (AN + DN) mechanism for DEP, with the formation of a phosphorane intermediate, having an overall reaction free energy and barrier of 11.5 and 43.0 kcal mol−1, respectively. In addition, ab initio molecular dynamics simulations were performed to investigate the stability of the phosphorane pentacoordinate intermediate observed in the reaction of the phosphate diester. The phosphorane intermediate has a lifetime of ∼1 ps after which it decomposes into the corresponding alcohol and phosphate monoester dianion. Electrostatics governs the interaction between the nucleophile and the phosphate ester. However, some degree of covalence in the interaction starts to appear at distances shorter than 2.45 Å for MEP and 2.63 Å for DEP. For the monoester, the electrostatic repulsive terms are the dominant contributions for the formation of the transition state. On the other hand, for the phosphate diester, the formation of the P–OH bond is dominated by associative terms of electrostatic nature.
local.identifier.orcidhttps://orcid.org/0000-0001-7543-5859
local.identifier.orcidhttps://orcid.org/0000-0001-6368-492X
local.identifier.orcidhttps://orcid.org/0000-0002-7783-3014
local.identifier.orcidhttps://orcid.org/0000-0002-0025-2158
local.publisher.countryBrasil
local.publisher.departmentICX - DEPARTAMENTO DE QUÍMICA
local.publisher.initialsUFMG
local.url.externahttps://pubs.rsc.org/en/content/articlelanding/2016/CP/C6CP01536K

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