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- Publisher Website: 10.1039/C4DT01491J
- Scopus: eid_2-s2.0-84908042411
- PMID: 25141046
- WOS: WOS:000343961000023
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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
Title | Mechanistic investigation of the cleavage of phosphodiester catalyzed by a symmetrical oxyimine-based macrocyclic dinuclear zinc complex: a DFT study |
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Authors | |
Issue Date | 2014 |
Publisher | Royal 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? |
Abstract | Density 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 Identifier | http://hdl.handle.net/10722/215099 |
ISSN | 2023 Impact Factor: 3.5 2023 SCImago Journal Rankings: 0.697 |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Zhang, X | - |
dc.contributor.author | Zheng, X | - |
dc.contributor.author | Phillips, DL | - |
dc.contributor.author | Zhao, C | - |
dc.date.accessioned | 2015-08-21T12:27:38Z | - |
dc.date.available | 2015-08-21T12:27:38Z | - |
dc.date.issued | 2014 | - |
dc.identifier.citation | Dalton Transactions, 2014, v. 43 n. 43, p. 16289-16299 | - |
dc.identifier.issn | 1477-9226 | - |
dc.identifier.uri | http://hdl.handle.net/10722/215099 | - |
dc.description.abstract | Density 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.language | eng | - |
dc.publisher | Royal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton | - |
dc.relation.ispartof | Dalton Transactions | - |
dc.title | Mechanistic investigation of the cleavage of phosphodiester catalyzed by a symmetrical oxyimine-based macrocyclic dinuclear zinc complex: a DFT study | - |
dc.type | Article | - |
dc.identifier.email | Phillips, DL: phillips@hku.hk | - |
dc.identifier.authority | Phillips, DL=rp00770 | - |
dc.identifier.doi | 10.1039/C4DT01491J | - |
dc.identifier.pmid | 25141046 | - |
dc.identifier.scopus | eid_2-s2.0-84908042411 | - |
dc.identifier.hkuros | 246413 | - |
dc.identifier.volume | 43 | - |
dc.identifier.issue | 43 | - |
dc.identifier.spage | 16289 | - |
dc.identifier.epage | 16299 | - |
dc.identifier.isi | WOS:000343961000023 | - |
dc.publisher.place | United Kingdom | - |
dc.identifier.issnl | 1477-9226 | - |