File Download

There are no files associated with this item.

  Links for fulltext
     (May Require Subscription)
Supplementary

Article: A Highly Oxidizing and Isolable Oxoruthenium(V) Complex [RuV(N4O)(O)]2+: Electronic Structure, Redox Properties, and Oxidation Reactions Investigated by DFT Calculations

TitleA Highly Oxidizing and Isolable Oxoruthenium(V) Complex [RuV(N4O)(O)]2+: Electronic Structure, Redox Properties, and Oxidation Reactions Investigated by DFT Calculations
Authors
KeywordsDensity functional calculations
Hydrochloric acid
Oxidation
Oxo complexes
Ruthenium
Issue Date2013
PublisherWiley - V C H Verlag GmbH & Co. KGaA. The Journal's web site is located at http://www.wiley-vch.de/publish/en/journals/alphabeticIndex/2451
Citation
Chemistry - An Asian Journal, 2013, v. 8 n. 9, p. 2046-2056 How to Cite?
AbstractThe electronic structure and redox properties of the highly oxidizing, isolable Ru(V)=O complex [Ru(V)(N4O)(O)](2+), its oxidation reactions with saturated alkanes (cyclohexane and methane) and inorganic substrates (hydrochloric acid and water), and its intermolecular coupling reaction have been examined by DFT calculations. The oxidation reactions with cyclohexane and methane proceed through hydrogen atom transfer in a transition state with a calculated free energy barrier of 10.8 and 23.8 kcal mol(-1), respectively. The overall free energy activation barrier (DeltaG( not equal)=25.5 kcal mol(-1)) of oxidation of hydrochloric acid can be decomposed into two parts: the formation of [Ru(III)(N4O)(HOCl)](2+) (DeltaG=15.0 kcal mol(-1)) and the substitution of HOCl by a water molecule (DeltaG( not equal)=10.5 kcal mol(-1)). For water oxidation, nucleophilic attack on Ru(V)=O by water, leading to O-O bond formation, has a free energy barrier of 24.0 kcal mol(-1), the major component of which comes from the cleavage of the H-OH bond of water. Intermolecular self-coupling of two molecules of [Ru(V)(N4O)(O)](2+) leads to the [(N4O)Ru(IV)-O2-Ru(III)(N4O)](4+) complex with a calculated free energy barrier of 12.0 kcal mol(-1).
Persistent Identifierhttp://hdl.handle.net/10722/202557
ISSN
2017 Impact Factor: 3.692
2015 SCImago Journal Rankings: 1.833
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorGuan, X-
dc.contributor.authorChan, SLF-
dc.contributor.authorChe, CM-
dc.date.accessioned2014-09-19T08:41:04Z-
dc.date.available2014-09-19T08:41:04Z-
dc.date.issued2013-
dc.identifier.citationChemistry - An Asian Journal, 2013, v. 8 n. 9, p. 2046-2056-
dc.identifier.issn1861-4728-
dc.identifier.urihttp://hdl.handle.net/10722/202557-
dc.description.abstractThe electronic structure and redox properties of the highly oxidizing, isolable Ru(V)=O complex [Ru(V)(N4O)(O)](2+), its oxidation reactions with saturated alkanes (cyclohexane and methane) and inorganic substrates (hydrochloric acid and water), and its intermolecular coupling reaction have been examined by DFT calculations. The oxidation reactions with cyclohexane and methane proceed through hydrogen atom transfer in a transition state with a calculated free energy barrier of 10.8 and 23.8 kcal mol(-1), respectively. The overall free energy activation barrier (DeltaG( not equal)=25.5 kcal mol(-1)) of oxidation of hydrochloric acid can be decomposed into two parts: the formation of [Ru(III)(N4O)(HOCl)](2+) (DeltaG=15.0 kcal mol(-1)) and the substitution of HOCl by a water molecule (DeltaG( not equal)=10.5 kcal mol(-1)). For water oxidation, nucleophilic attack on Ru(V)=O by water, leading to O-O bond formation, has a free energy barrier of 24.0 kcal mol(-1), the major component of which comes from the cleavage of the H-OH bond of water. Intermolecular self-coupling of two molecules of [Ru(V)(N4O)(O)](2+) leads to the [(N4O)Ru(IV)-O2-Ru(III)(N4O)](4+) complex with a calculated free energy barrier of 12.0 kcal mol(-1).-
dc.languageeng-
dc.publisherWiley - V C H Verlag GmbH & Co. KGaA. The Journal's web site is located at http://www.wiley-vch.de/publish/en/journals/alphabeticIndex/2451-
dc.relation.ispartofChemistry - An Asian Journal-
dc.subjectDensity functional calculations-
dc.subjectHydrochloric acid-
dc.subjectOxidation-
dc.subjectOxo complexes-
dc.subjectRuthenium-
dc.titleA Highly Oxidizing and Isolable Oxoruthenium(V) Complex [RuV(N4O)(O)]2+: Electronic Structure, Redox Properties, and Oxidation Reactions Investigated by DFT Calculations-
dc.typeArticle-
dc.identifier.emailGuan, X: xgguan@hku.hk-
dc.identifier.emailChe, CM: cmche@hku.hk-
dc.identifier.authorityChe, CM=rp00670-
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/asia.201300458-
dc.identifier.pmid23788366-
dc.identifier.scopuseid_2-s2.0-84883228347-
dc.identifier.hkuros236533-
dc.identifier.volume8-
dc.identifier.issue9-
dc.identifier.spage2046-
dc.identifier.epage2056-
dc.identifier.isiWOS:000325928700016-
dc.publisher.placeGermany-

Export via OAI-PMH Interface in XML Formats


OR


Export to Other Non-XML Formats