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Article: Unraveling mechanisms of the uncoordinated nucleophiles: theoretical elucidations of the cleavage of bis(p-nitrophenyl) phosphate mediated by zinc-complexes with apical nucleophiles

TitleUnraveling mechanisms of the uncoordinated nucleophiles: theoretical elucidations of the cleavage of bis(p-nitrophenyl) phosphate mediated by zinc-complexes with apical nucleophiles
Authors
KeywordsDimerization
Ligands
Molecules
Nucleophiles
Alternative solvents
Issue Date2019
PublisherRoyal Society of Chemistry: Open Access. The Journal's web site is located at http://pubs.rsc.org/en/journals/journalissues/ra
Citation
RSC Advances, 2019, v. 9 n. 65, p. 37696-37704 How to Cite?
AbstractA theoretical approach was used to investigate the hydrolytic cleavage mechanisms of the bis(p-nitrophenyl) phosphate (BNPP−) catalyzed by Zn(II)-complexes featuring uncoordinated nucleophiles. Ligand-based and alternative solvent-based nucleophilic attack reaction models are proposed. The pKa values of the Zn(II)-bound water molecules or ligands in the [Zn(LnH)(η-H2O)(H2O)]2+ (n = 1, 2 and 3) complexes, as well as the dimerization tendency of the mononuclear Zn(II)-complexes, were found to significantly influence the reaction mechanisms. The Zn(II)-L3 complexes were found to be more favorable for the hydrolytic cleavage of the BNPP− via a ligand-based nucleophilic attack pathway. This was due to the lower pKa value for the deprotonation of the oxime ligand, the hard dimerization of the mononuclear Zn(II)-L3 species, and the presence of an uncoordinated nucleophile. The origins of the uncoordinated reactions were systematically elucidated. The theoretical results reported here are in good agreement with experimental observations and more importantly, help to elucidate the factors that influence intermolecular nucleophilic attack reactions with coordinated/uncoordinated nucleophiles.
Persistent Identifierhttp://hdl.handle.net/10722/286170
ISSN
2018 Impact Factor: 3.049
2015 SCImago Journal Rankings: 0.990

 

DC FieldValueLanguage
dc.contributor.authorZhou, X-
dc.contributor.authorZhang, XP-
dc.contributor.authorLi, W-
dc.contributor.authorJiang, JX-
dc.contributor.authorXu, H-
dc.contributor.authorKe, Z-
dc.contributor.authorPhillips, DL-
dc.contributor.authorZhao, C-
dc.date.accessioned2020-08-31T07:00:07Z-
dc.date.available2020-08-31T07:00:07Z-
dc.date.issued2019-
dc.identifier.citationRSC Advances, 2019, v. 9 n. 65, p. 37696-37704-
dc.identifier.issn2046-2069-
dc.identifier.urihttp://hdl.handle.net/10722/286170-
dc.description.abstractA theoretical approach was used to investigate the hydrolytic cleavage mechanisms of the bis(p-nitrophenyl) phosphate (BNPP−) catalyzed by Zn(II)-complexes featuring uncoordinated nucleophiles. Ligand-based and alternative solvent-based nucleophilic attack reaction models are proposed. The pKa values of the Zn(II)-bound water molecules or ligands in the [Zn(LnH)(η-H2O)(H2O)]2+ (n = 1, 2 and 3) complexes, as well as the dimerization tendency of the mononuclear Zn(II)-complexes, were found to significantly influence the reaction mechanisms. The Zn(II)-L3 complexes were found to be more favorable for the hydrolytic cleavage of the BNPP− via a ligand-based nucleophilic attack pathway. This was due to the lower pKa value for the deprotonation of the oxime ligand, the hard dimerization of the mononuclear Zn(II)-L3 species, and the presence of an uncoordinated nucleophile. The origins of the uncoordinated reactions were systematically elucidated. The theoretical results reported here are in good agreement with experimental observations and more importantly, help to elucidate the factors that influence intermolecular nucleophilic attack reactions with coordinated/uncoordinated nucleophiles.-
dc.languageeng-
dc.publisherRoyal Society of Chemistry: Open Access. The Journal's web site is located at http://pubs.rsc.org/en/journals/journalissues/ra-
dc.relation.ispartofRSC Advances-
dc.rightsThis work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.-
dc.subjectDimerization-
dc.subjectLigands-
dc.subjectMolecules-
dc.subjectNucleophiles-
dc.subjectAlternative solvents-
dc.titleUnraveling mechanisms of the uncoordinated nucleophiles: theoretical elucidations of the cleavage of bis(p-nitrophenyl) phosphate mediated by zinc-complexes with apical nucleophiles-
dc.typeArticle-
dc.identifier.emailPhillips, DL: phillips@hku.hk-
dc.identifier.authorityPhillips, DL=rp00770-
dc.description.naturepublished_or_final_version-
dc.identifier.doi10.1039/C9RA06737J-
dc.identifier.scopuseid_2-s2.0-85075720230-
dc.identifier.hkuros313791-
dc.identifier.volume9-
dc.identifier.issue65-
dc.identifier.spage37696-
dc.identifier.epage37704-
dc.publisher.placeUnited Kingdom-

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