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Article: A kinetic study on the reactivity of a cis-dioxoruthenium(VI) complex. Oxidation of alcohols, aromatic hydrocarbons, and alkenes by cis-[RuVI(Tet-Me6)O2]2+

TitleA kinetic study on the reactivity of a cis-dioxoruthenium(VI) complex. Oxidation of alcohols, aromatic hydrocarbons, and alkenes by cis-[RuVI(Tet-Me6)O2]2+
Authors
Issue Date1995
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/joc
Citation
Journal Of Organic Chemistry, 1995, v. 60 n. 21, p. 6840-6846 How to Cite?
AbstractThe kinetics of oxidation of alcohols, aromatic hydrocarbons, and alkenes by cis-[RuVI(Tet-Me6)-O2]2+ (Tet-Me6 = N,N,N′,N′-tetramethyl-3,6-diazaoctane-1,8-diamine) have been studied. In general, the oxidation chemistry of cis-[RuVI(Tet-Me6)O2]2+ is similar to those of trans-dioxoruthenium(VI) compounds such as trans-[RuVI(N2O2)O2]2+ (N2O2 = 1,12-dimethyl-3,4:9,10-dibenzo-1,12-diaza-5,8-dioxacyclopentadecane) and trans-[RuVI(pytn)O2]2+ (pytn = N,N′-dimethylbis(2-pyridylmethyl)-propylenediamine). The oxidation is first-order with respect to cis-[RuVI(Tet-Me6)O2]2+ and organic substrates and is accompanied by large and negative ΔS‡. Large kH/kD values were found for the oxidation of alcohols. A linear Hammett plot for the oxidation of para-substituted benzyl alcohols with a slope of -1.0 was obtained. For alcohol oxidation, a charge-transfer mechanism involving hydride abstraction has been proposed. Oxidation of toluene, ethylbenzene, and cumene by cis-[RuVI(Tet-Me6)O2]2+ gave benzaldehyde, acetophenone/sec-phenylisopropyl alcohol, and 2-phenyl-isopropyl alcohol, respectively. A kH/kD value of 11 has been found for the oxidation of ethylbenzene. In the oxidation of these aromatic hydrocarbons, the key step likely involves C-H bond activation in the transition state. Allylic oxidation is the major reaction pathway in the cyclohexene oxidation. In the oxidation of alkenes, both C=C bond cleavage product(s) and epoxides were found. The Hammett plot for the oxidation of para-substituted styrenes is linear with a slope of -2.0. The oxidation likely proceeds through a charge-transfer mechanism. © 1995 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/167266
ISSN
2015 Impact Factor: 4.785
2015 SCImago Journal Rankings: 2.095
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorCheng, WCen_US
dc.contributor.authorYu, WYen_US
dc.contributor.authorLi, CKen_US
dc.contributor.authorChe, CMen_US
dc.date.accessioned2012-10-08T03:05:02Z-
dc.date.available2012-10-08T03:05:02Z-
dc.date.issued1995en_US
dc.identifier.citationJournal Of Organic Chemistry, 1995, v. 60 n. 21, p. 6840-6846en_US
dc.identifier.issn0022-3263en_US
dc.identifier.urihttp://hdl.handle.net/10722/167266-
dc.description.abstractThe kinetics of oxidation of alcohols, aromatic hydrocarbons, and alkenes by cis-[RuVI(Tet-Me6)-O2]2+ (Tet-Me6 = N,N,N′,N′-tetramethyl-3,6-diazaoctane-1,8-diamine) have been studied. In general, the oxidation chemistry of cis-[RuVI(Tet-Me6)O2]2+ is similar to those of trans-dioxoruthenium(VI) compounds such as trans-[RuVI(N2O2)O2]2+ (N2O2 = 1,12-dimethyl-3,4:9,10-dibenzo-1,12-diaza-5,8-dioxacyclopentadecane) and trans-[RuVI(pytn)O2]2+ (pytn = N,N′-dimethylbis(2-pyridylmethyl)-propylenediamine). The oxidation is first-order with respect to cis-[RuVI(Tet-Me6)O2]2+ and organic substrates and is accompanied by large and negative ΔS‡. Large kH/kD values were found for the oxidation of alcohols. A linear Hammett plot for the oxidation of para-substituted benzyl alcohols with a slope of -1.0 was obtained. For alcohol oxidation, a charge-transfer mechanism involving hydride abstraction has been proposed. Oxidation of toluene, ethylbenzene, and cumene by cis-[RuVI(Tet-Me6)O2]2+ gave benzaldehyde, acetophenone/sec-phenylisopropyl alcohol, and 2-phenyl-isopropyl alcohol, respectively. A kH/kD value of 11 has been found for the oxidation of ethylbenzene. In the oxidation of these aromatic hydrocarbons, the key step likely involves C-H bond activation in the transition state. Allylic oxidation is the major reaction pathway in the cyclohexene oxidation. In the oxidation of alkenes, both C=C bond cleavage product(s) and epoxides were found. The Hammett plot for the oxidation of para-substituted styrenes is linear with a slope of -2.0. The oxidation likely proceeds through a charge-transfer mechanism. © 1995 American Chemical Society.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jocen_US
dc.relation.ispartofJournal of Organic Chemistryen_US
dc.titleA kinetic study on the reactivity of a cis-dioxoruthenium(VI) complex. Oxidation of alcohols, aromatic hydrocarbons, and alkenes by cis-[RuVI(Tet-Me6)O2]2+en_US
dc.typeArticleen_US
dc.identifier.emailChe, CM:cmche@hku.hken_US
dc.identifier.authorityChe, CM=rp00670en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/jo00126a038-
dc.identifier.scopuseid_2-s2.0-0000337354en_US
dc.identifier.volume60en_US
dc.identifier.issue21en_US
dc.identifier.spage6840en_US
dc.identifier.epage6846en_US
dc.identifier.isiWOS:A1995TB90000038-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridCheng, WC=7402169293en_US
dc.identifier.scopusauthoridYu, WY=7403913673en_US
dc.identifier.scopusauthoridLi, CK=15067432700en_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US

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