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Article: Mechanistic Investigation into the Cleavage of a Phosphomonoester Mediated by a Symmetrical Oxyimine-Based Macrocyclic Zinc(II) Complex

TitleMechanistic Investigation into the Cleavage of a Phosphomonoester Mediated by a Symmetrical Oxyimine-Based Macrocyclic Zinc(II) Complex
Authors
Issue Date2014
Citation
ChemPhysChem, 2014, v. 15, p. 1887-1898 How to Cite?
AbstractDensity functional calculations are utilized to explore the hydrolysis mechanisms of the phosphomonoester 4-nitrophenyl phosphate catalyzed by a symmetrical zinc(II) complex. The formation process and properties of the active catalyst are verified. Eight plausible mechanisms are proposed and categorized into three groups. All of the proposed mechanisms, except for Mechanism 7 (see text), are SN2-type addition–substitution reaction pathways. Nucleophilic attack at the ortho position occurs in Mechanism 7 with a relatively high reaction barrier. Mechanisms 1 and 2 in the monocatalyst model, Mechanisms 5 to 7 in the sandwich-dual-catalyst model, as well as the nucleophilic addition–substitution step in Mechanism 8 are concerted reaction pathways, whereas the rest appear to occur in a stepwise manner. Meanwhile, the explicit solvent model is utilized to consider direct hydrogen bonds and solvation interactions and these results indicate that the added water molecule is involved in the hydrolysis process, but does not change the mechanisms significantly. Mechanism 8, with the lowest reaction barrier, is the most favored reaction pathway of the eight proposed mechanisms, although Mechanisms 1, 4, and 6 are in competition with Mechanism 8. In consideration of the zinc(II) complex concentration, Mechanism 1 is only the predominant reaction pathway at a low zinc(II) complex concentration; Mechanisms 4 and 6 tend to be more competitive with increasing concentration of the zinc(II) complexes, and Mechanism 8 is favored at high zinc(II) complex concentrations. Our calculated results are consistent with, and can be used to systematically interpret, experimental observations. More importantly, insightful suggestions are made regarding the catalyst design and selection of the reaction environment.
Persistent Identifierhttp://hdl.handle.net/10722/202576
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorZhang, Xen_US
dc.contributor.authorXu, Xen_US
dc.contributor.authorXu, Hen_US
dc.contributor.authorZhang, Xen_US
dc.contributor.authorPhillips, DLen_US
dc.contributor.authorZhao, Cen_US
dc.date.accessioned2014-09-19T08:41:36Z-
dc.date.available2014-09-19T08:41:36Z-
dc.date.issued2014en_US
dc.identifier.citationChemPhysChem, 2014, v. 15, p. 1887-1898en_US
dc.identifier.urihttp://hdl.handle.net/10722/202576-
dc.description.abstractDensity functional calculations are utilized to explore the hydrolysis mechanisms of the phosphomonoester 4-nitrophenyl phosphate catalyzed by a symmetrical zinc(II) complex. The formation process and properties of the active catalyst are verified. Eight plausible mechanisms are proposed and categorized into three groups. All of the proposed mechanisms, except for Mechanism 7 (see text), are SN2-type addition–substitution reaction pathways. Nucleophilic attack at the ortho position occurs in Mechanism 7 with a relatively high reaction barrier. Mechanisms 1 and 2 in the monocatalyst model, Mechanisms 5 to 7 in the sandwich-dual-catalyst model, as well as the nucleophilic addition–substitution step in Mechanism 8 are concerted reaction pathways, whereas the rest appear to occur in a stepwise manner. Meanwhile, the explicit solvent model is utilized to consider direct hydrogen bonds and solvation interactions and these results indicate that the added water molecule is involved in the hydrolysis process, but does not change the mechanisms significantly. Mechanism 8, with the lowest reaction barrier, is the most favored reaction pathway of the eight proposed mechanisms, although Mechanisms 1, 4, and 6 are in competition with Mechanism 8. In consideration of the zinc(II) complex concentration, Mechanism 1 is only the predominant reaction pathway at a low zinc(II) complex concentration; Mechanisms 4 and 6 tend to be more competitive with increasing concentration of the zinc(II) complexes, and Mechanism 8 is favored at high zinc(II) complex concentrations. Our calculated results are consistent with, and can be used to systematically interpret, experimental observations. More importantly, insightful suggestions are made regarding the catalyst design and selection of the reaction environment.en_US
dc.languageengen_US
dc.relation.ispartofChemPhysChemen_US
dc.titleMechanistic Investigation into the Cleavage of a Phosphomonoester Mediated by a Symmetrical Oxyimine-Based Macrocyclic Zinc(II) Complexen_US
dc.typeArticleen_US
dc.identifier.emailPhillips, DL: phillips@hku.hken_US
dc.identifier.authorityPhillips, DL=rp00770en_US
dc.identifier.doi10.1002/cphc.201301216en_US
dc.identifier.pmid24692392-
dc.identifier.hkuros237047en_US
dc.identifier.volume15en_US
dc.identifier.spage1887en_US
dc.identifier.epage1898en_US
dc.identifier.isiWOS:000338012700020-

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