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Article: Stoichiometric oxidations of σ-bonds: Radical and possible non-radical pathways
Title | Stoichiometric oxidations of σ-bonds: Radical and possible non-radical pathways |
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Authors | |
Keywords | Hydrogen-Atom Abstraction Marcus Theory Osmium Tetroxide Oxidation Radicals |
Issue Date | 2006 |
Publisher | Elsevier 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? |
Abstract | Many 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 Identifier | http://hdl.handle.net/10722/168013 |
ISSN | 2018 Impact Factor: 5.008 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
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dc.contributor.author | Mayer, JM | en_US |
dc.contributor.author | Mader, EA | en_US |
dc.contributor.author | Roth, JP | en_US |
dc.contributor.author | Bryant, JR | en_US |
dc.contributor.author | Matsuo, T | en_US |
dc.contributor.author | Dehestani, A | en_US |
dc.contributor.author | Bales, BC | en_US |
dc.contributor.author | Watson, EJ | en_US |
dc.contributor.author | Osako, T | en_US |
dc.contributor.author | ValliantSaunders, K | en_US |
dc.contributor.author | Lam, WH | en_US |
dc.contributor.author | Hrovat, DA | en_US |
dc.contributor.author | Borden, WT | en_US |
dc.contributor.author | Davidson, ER | en_US |
dc.date.accessioned | 2012-10-08T03:14:08Z | - |
dc.date.available | 2012-10-08T03:14:08Z | - |
dc.date.issued | 2006 | en_US |
dc.identifier.citation | Journal Of Molecular Catalysis A: Chemical, 2006, v. 251 n. 1-2, p. 24-33 | en_US |
dc.identifier.issn | 1381-1169 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/168013 | - |
dc.description.abstract | Many 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.language | eng | en_US |
dc.publisher | Elsevier BV. The Journal's web site is located at http://www.elsevier.com/locate/molcata | en_US |
dc.relation.ispartof | Journal of Molecular Catalysis A: Chemical | en_US |
dc.subject | Hydrogen-Atom Abstraction | en_US |
dc.subject | Marcus Theory | en_US |
dc.subject | Osmium Tetroxide | en_US |
dc.subject | Oxidation | en_US |
dc.subject | Radicals | en_US |
dc.title | Stoichiometric oxidations of σ-bonds: Radical and possible non-radical pathways | en_US |
dc.type | Article | en_US |
dc.identifier.email | Lam, WH:chsue@hku.hk | en_US |
dc.identifier.authority | Lam, WH=rp00719 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1016/j.molcata.2006.02.010 | en_US |
dc.identifier.scopus | eid_2-s2.0-33646108107 | en_US |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-33646108107&selection=ref&src=s&origin=recordpage | en_US |
dc.identifier.volume | 251 | en_US |
dc.identifier.issue | 1-2 | en_US |
dc.identifier.spage | 24 | en_US |
dc.identifier.epage | 33 | en_US |
dc.identifier.isi | WOS:000237617200004 | - |
dc.publisher.place | Netherlands | en_US |
dc.identifier.scopusauthorid | Mayer, JM=7403140693 | en_US |
dc.identifier.scopusauthorid | Mader, EA=7005899029 | en_US |
dc.identifier.scopusauthorid | Roth, JP=7404379922 | en_US |
dc.identifier.scopusauthorid | Bryant, JR=7202903917 | en_US |
dc.identifier.scopusauthorid | Matsuo, T=7403703269 | en_US |
dc.identifier.scopusauthorid | Dehestani, A=6505851528 | en_US |
dc.identifier.scopusauthorid | Bales, BC=7003520391 | en_US |
dc.identifier.scopusauthorid | Watson, EJ=7203063691 | en_US |
dc.identifier.scopusauthorid | Osako, T=6603996043 | en_US |
dc.identifier.scopusauthorid | ValliantSaunders, K=13103018900 | en_US |
dc.identifier.scopusauthorid | Lam, WH=26642862800 | en_US |
dc.identifier.scopusauthorid | Hrovat, DA=7005268670 | en_US |
dc.identifier.scopusauthorid | Borden, WT=35495118300 | en_US |
dc.identifier.scopusauthorid | Davidson, ER=7402237753 | en_US |
dc.identifier.issnl | 1381-1169 | - |