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Article: Mechanistic investigation of the cleavage of phosphodiester catalyzed by a symmetrical oxyimine-based macrocyclic dinuclear zinc complex: a DFT study

TitleMechanistic investigation of the cleavage of phosphodiester catalyzed by a symmetrical oxyimine-based macrocyclic dinuclear zinc complex: a DFT study
Authors
Issue Date2014
PublisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton
Citation
Dalton Transactions, 2014, v. 43 n. 43, p. 16289-16299 How to Cite?
AbstractDensity functional theory (DFT) was utilized to investigate the hydrolysis reaction mechanisms of phosphodiester BNPP (BNPP = bis(4-nitrophenyl)phosphate) catalyzed by a symmetrical oxyimine-based macrocyclic dinuclear zinc(II) complex. We examined the nature of the nucleophilic reagent and the active form of the catalyst. The coordination and binding models of the catalyst–substrate complex were explored and we investigated two catalyst configurations (a ridge configuration and a plane configuration), four basic catalyst–substrate binding models (a mono-point-binding model, a dual-point-binding model, an OH-bridging model and a mono-center-dual-binding model) and two alternate roles for the metal-coordinated hydroxide ion (whether it acts as a nucleophile or as a general base to facilitate the deprotonation of a solvent molecule). The one-point-binding mode was found to be preferred to construct a starting reactant. Nine plausible reaction mechanisms were proposed and investigated. Mechanism 1, a stepwise SN2-type addition–substitution reaction involving a para-position nucleophilic attack and the configuration inversion of the phosphate, was found to be the most favorable pathway. All of the proposed pathways are derived from alternate mechanisms such as a ping-pong mechanism and an AP mechanism. The ping-pong mechanism in combination with the role of the metal-coordinated hydroxide ion acting as a nucleophile was found to be more competitive than the other mechanisms examined. Results reported in this paper are consistent with, and can be utilized to systematically interpret, the experimental observations in the literature.
Persistent Identifierhttp://hdl.handle.net/10722/215099
ISSN
2015 Impact Factor: 4.177
2015 SCImago Journal Rankings: 1.404

 

DC FieldValueLanguage
dc.contributor.authorZhang, X-
dc.contributor.authorZheng, X-
dc.contributor.authorPhillips, DL-
dc.contributor.authorZhao, C-
dc.date.accessioned2015-08-21T12:27:38Z-
dc.date.available2015-08-21T12:27:38Z-
dc.date.issued2014-
dc.identifier.citationDalton Transactions, 2014, v. 43 n. 43, p. 16289-16299-
dc.identifier.issn1477-9226-
dc.identifier.urihttp://hdl.handle.net/10722/215099-
dc.description.abstractDensity functional theory (DFT) was utilized to investigate the hydrolysis reaction mechanisms of phosphodiester BNPP (BNPP = bis(4-nitrophenyl)phosphate) catalyzed by a symmetrical oxyimine-based macrocyclic dinuclear zinc(II) complex. We examined the nature of the nucleophilic reagent and the active form of the catalyst. The coordination and binding models of the catalyst–substrate complex were explored and we investigated two catalyst configurations (a ridge configuration and a plane configuration), four basic catalyst–substrate binding models (a mono-point-binding model, a dual-point-binding model, an OH-bridging model and a mono-center-dual-binding model) and two alternate roles for the metal-coordinated hydroxide ion (whether it acts as a nucleophile or as a general base to facilitate the deprotonation of a solvent molecule). The one-point-binding mode was found to be preferred to construct a starting reactant. Nine plausible reaction mechanisms were proposed and investigated. Mechanism 1, a stepwise SN2-type addition–substitution reaction involving a para-position nucleophilic attack and the configuration inversion of the phosphate, was found to be the most favorable pathway. All of the proposed pathways are derived from alternate mechanisms such as a ping-pong mechanism and an AP mechanism. The ping-pong mechanism in combination with the role of the metal-coordinated hydroxide ion acting as a nucleophile was found to be more competitive than the other mechanisms examined. Results reported in this paper are consistent with, and can be utilized to systematically interpret, the experimental observations in the literature.-
dc.languageeng-
dc.publisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton-
dc.relation.ispartofDalton Transactions-
dc.titleMechanistic investigation of the cleavage of phosphodiester catalyzed by a symmetrical oxyimine-based macrocyclic dinuclear zinc complex: a DFT study-
dc.typeArticle-
dc.identifier.emailPhillips, DL: phillips@hku.hk-
dc.identifier.authorityPhillips, DL=rp00770-
dc.identifier.doi10.1039/C4DT01491J-
dc.identifier.pmid25141046-
dc.identifier.hkuros246413-
dc.identifier.volume43-
dc.identifier.issue43-
dc.identifier.spage16289-
dc.identifier.epage16299-
dc.publisher.placeUnited Kingdom-

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