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Article: Stoichiometric oxidations of σ-bonds: Radical and possible non-radical pathways

TitleStoichiometric oxidations of σ-bonds: Radical and possible non-radical pathways
Authors
KeywordsHydrogen-Atom Abstraction
Marcus Theory
Osmium Tetroxide
Oxidation
Radicals
Issue Date2006
PublisherElsevier BV. The Journal's web site is located at http://www.elsevier.com/locate/molcata
Citation
Journal Of Molecular Catalysis A: Chemical, 2006, v. 251 n. 1-2, p. 24-33 How to Cite?
AbstractMany transition metal complexes accomplish or catalyze the oxidation of C{single bond}H, O{single bond}H, and other σ-bonds. Under aerobic conditions, metal complexes typically modulate an autoxidation radical chain. In anaerobic reactions, a metal complex can be the reactive species that attacks the σ-bond, in many cases by abstracting a hydrogen atom from the substrate. Examples described here include the oxidation of alkylaromatic compounds by ruthenium oxo complexes and reactions of deprotonated iron(III) complexes. In general, these reactions occur with addition of H+ to a ligand and e- to the metal center. Rate constants for such hydrogen-atom transfer reactions can, in many cases, be predicted by the Marcus cross relation. Autoxidation and metal-mediated radical mechanisms are so prevalent that proposals of non-radical oxidations of C{single bond}H bonds carry a higher burden of proof. It is argued here that the oxidation of H2 by OsO4 occurs by a non-radical, [3 + 2] mechanism. OsO4 oxidizes alkanes under similar aqueous conditions. For example, isobutane is oxidized to tert-butanol, and cyclohexane to adipate and succinate. The alkane oxidations do not have the hallmarks of a radical mechanism but sufficient questions remain that a radical pathway cannot be excluded at this time. © 2006 Elsevier B.V. All rights reserved.
Persistent Identifierhttp://hdl.handle.net/10722/168013
ISSN
2015 Impact Factor: 3.958
2015 SCImago Journal Rankings: 1.072
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorMayer, JMen_US
dc.contributor.authorMader, EAen_US
dc.contributor.authorRoth, JPen_US
dc.contributor.authorBryant, JRen_US
dc.contributor.authorMatsuo, Ten_US
dc.contributor.authorDehestani, Aen_US
dc.contributor.authorBales, BCen_US
dc.contributor.authorWatson, EJen_US
dc.contributor.authorOsako, Ten_US
dc.contributor.authorValliantSaunders, Ken_US
dc.contributor.authorLam, WHen_US
dc.contributor.authorHrovat, DAen_US
dc.contributor.authorBorden, WTen_US
dc.contributor.authorDavidson, ERen_US
dc.date.accessioned2012-10-08T03:14:08Z-
dc.date.available2012-10-08T03:14:08Z-
dc.date.issued2006en_US
dc.identifier.citationJournal Of Molecular Catalysis A: Chemical, 2006, v. 251 n. 1-2, p. 24-33en_US
dc.identifier.issn1381-1169en_US
dc.identifier.urihttp://hdl.handle.net/10722/168013-
dc.description.abstractMany transition metal complexes accomplish or catalyze the oxidation of C{single bond}H, O{single bond}H, and other σ-bonds. Under aerobic conditions, metal complexes typically modulate an autoxidation radical chain. In anaerobic reactions, a metal complex can be the reactive species that attacks the σ-bond, in many cases by abstracting a hydrogen atom from the substrate. Examples described here include the oxidation of alkylaromatic compounds by ruthenium oxo complexes and reactions of deprotonated iron(III) complexes. In general, these reactions occur with addition of H+ to a ligand and e- to the metal center. Rate constants for such hydrogen-atom transfer reactions can, in many cases, be predicted by the Marcus cross relation. Autoxidation and metal-mediated radical mechanisms are so prevalent that proposals of non-radical oxidations of C{single bond}H bonds carry a higher burden of proof. It is argued here that the oxidation of H2 by OsO4 occurs by a non-radical, [3 + 2] mechanism. OsO4 oxidizes alkanes under similar aqueous conditions. For example, isobutane is oxidized to tert-butanol, and cyclohexane to adipate and succinate. The alkane oxidations do not have the hallmarks of a radical mechanism but sufficient questions remain that a radical pathway cannot be excluded at this time. © 2006 Elsevier B.V. All rights reserved.en_US
dc.languageengen_US
dc.publisherElsevier BV. The Journal's web site is located at http://www.elsevier.com/locate/molcataen_US
dc.relation.ispartofJournal of Molecular Catalysis A: Chemicalen_US
dc.subjectHydrogen-Atom Abstractionen_US
dc.subjectMarcus Theoryen_US
dc.subjectOsmium Tetroxideen_US
dc.subjectOxidationen_US
dc.subjectRadicalsen_US
dc.titleStoichiometric oxidations of σ-bonds: Radical and possible non-radical pathwaysen_US
dc.typeArticleen_US
dc.identifier.emailLam, WH:chsue@hku.hken_US
dc.identifier.authorityLam, WH=rp00719en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1016/j.molcata.2006.02.010en_US
dc.identifier.scopuseid_2-s2.0-33646108107en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-33646108107&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume251en_US
dc.identifier.issue1-2en_US
dc.identifier.spage24en_US
dc.identifier.epage33en_US
dc.identifier.isiWOS:000237617200004-
dc.publisher.placeNetherlandsen_US
dc.identifier.scopusauthoridMayer, JM=7403140693en_US
dc.identifier.scopusauthoridMader, EA=7005899029en_US
dc.identifier.scopusauthoridRoth, JP=7404379922en_US
dc.identifier.scopusauthoridBryant, JR=7202903917en_US
dc.identifier.scopusauthoridMatsuo, T=7403703269en_US
dc.identifier.scopusauthoridDehestani, A=6505851528en_US
dc.identifier.scopusauthoridBales, BC=7003520391en_US
dc.identifier.scopusauthoridWatson, EJ=7203063691en_US
dc.identifier.scopusauthoridOsako, T=6603996043en_US
dc.identifier.scopusauthoridValliantSaunders, K=13103018900en_US
dc.identifier.scopusauthoridLam, WH=26642862800en_US
dc.identifier.scopusauthoridHrovat, DA=7005268670en_US
dc.identifier.scopusauthoridBorden, WT=35495118300en_US
dc.identifier.scopusauthoridDavidson, ER=7402237753en_US

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