File Download

There are no files associated with this item.

  Links for fulltext
     (May Require Subscription)
Supplementary

Article: Kinetics and Mechanism of the Oxidation of Alkylaromatic Compounds by a trans-Dioxoruthenium(VI) Complex

TitleKinetics and Mechanism of the Oxidation of Alkylaromatic Compounds by a trans-Dioxoruthenium(VI) Complex
Authors
Issue Date2003
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 2003, v. 42 n. 24, p. 8011-8018 How to Cite?
AbstractThe oxidations of a series of 21 alkylaromatic compounds by trans-[Ru VI(L)(O) 2] 2+ (L = 1,12-dimethyl-3,4:9,10-dibenzo-1,12-diaza-5,8-dioxacyclopentadecane) have been studied in CH 3CN. Toluene is oxidized to benzaldehyde and a small amount of benzyl alcohol. 9,10-Dihydroanthracene is oxidized to anthracene and anthraquinone. Other substrates give oxygenated products. The kinetics of the reactions were monitored by UV-vis spectrophotometry, and the rate law is: -d[R VI]/dt = k 2[Ru VI][ArCH 3]. The kinetic isotope effects for the oxidation of toluene/d 8-toluene and fluorene/d 10-fluorene are 15 and 10.5, respectively. A plot of ΔH‡ versus ΔS‡ is linear, suggesting a common mechanism for all the substrates. In the oxidation of para-substituted toluenes, a linear correlation between log k 2 and σ 0 values is observed, consistent with a benzyl radical intermediate. A linear correlation between ΔG‡ and ΔH 0 (the difference between the strength of the bond being broken and that being formed in a H-atom transfer step) is also found, which strongly supports a hydrogen atom transfer mechanism for the oxidation of these substrates by trans-[Ru VI(L)(O) 2] 2+. The slope of (0.61 ± 0.06) is in reasonable agreement with the theoretical slope of 0.5 predicted by Marcus theory.
Persistent Identifierhttp://hdl.handle.net/10722/69361
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLam, WWYen_HK
dc.contributor.authorYiu, SMen_HK
dc.contributor.authorYiu, DTYen_HK
dc.contributor.authorLau, TCen_HK
dc.contributor.authorYip, WPen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2010-09-06T06:12:57Z-
dc.date.available2010-09-06T06:12:57Z-
dc.date.issued2003en_HK
dc.identifier.citationInorganic Chemistry, 2003, v. 42 n. 24, p. 8011-8018en_HK
dc.identifier.issn0020-1669en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69361-
dc.description.abstractThe oxidations of a series of 21 alkylaromatic compounds by trans-[Ru VI(L)(O) 2] 2+ (L = 1,12-dimethyl-3,4:9,10-dibenzo-1,12-diaza-5,8-dioxacyclopentadecane) have been studied in CH 3CN. Toluene is oxidized to benzaldehyde and a small amount of benzyl alcohol. 9,10-Dihydroanthracene is oxidized to anthracene and anthraquinone. Other substrates give oxygenated products. The kinetics of the reactions were monitored by UV-vis spectrophotometry, and the rate law is: -d[R VI]/dt = k 2[Ru VI][ArCH 3]. The kinetic isotope effects for the oxidation of toluene/d 8-toluene and fluorene/d 10-fluorene are 15 and 10.5, respectively. A plot of ΔH‡ versus ΔS‡ is linear, suggesting a common mechanism for all the substrates. In the oxidation of para-substituted toluenes, a linear correlation between log k 2 and σ 0 values is observed, consistent with a benzyl radical intermediate. A linear correlation between ΔG‡ and ΔH 0 (the difference between the strength of the bond being broken and that being formed in a H-atom transfer step) is also found, which strongly supports a hydrogen atom transfer mechanism for the oxidation of these substrates by trans-[Ru VI(L)(O) 2] 2+. The slope of (0.61 ± 0.06) is in reasonable agreement with the theoretical slope of 0.5 predicted by Marcus theory.en_HK
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_HK
dc.relation.ispartofInorganic Chemistryen_HK
dc.titleKinetics and Mechanism of the Oxidation of Alkylaromatic Compounds by a trans-Dioxoruthenium(VI) Complexen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0020-1669&volume=42&spage=8011&epage=8018&date=2003&atitle=Kinetics+and+mechanism+of+the+oxidation+of+alkylaromatic+compounds+by+a+trans-dioxoruthenium(VI)+complexen_HK
dc.identifier.emailChe, CM:cmche@hku.hken_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ic034782jen_HK
dc.identifier.scopuseid_2-s2.0-0345448375en_HK
dc.identifier.hkuros94125en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0345448375&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume42en_HK
dc.identifier.issue24en_HK
dc.identifier.spage8011en_HK
dc.identifier.epage8018en_HK
dc.identifier.isiWOS:000186833900047-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridLam, WWY=21733437300en_HK
dc.identifier.scopusauthoridYiu, SM=43462142100en_HK
dc.identifier.scopusauthoridYiu, DTY=6603285427en_HK
dc.identifier.scopusauthoridLau, TC=7102222310en_HK
dc.identifier.scopusauthoridYip, WP=8751048200en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

Export via OAI-PMH Interface in XML Formats


OR


Export to Other Non-XML Formats