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Article: Kinetics of alkene oxidation by cationic trans-dioxoruthenium(VI) complexes. Effect of driving force on rate constants

TitleKinetics of alkene oxidation by cationic trans-dioxoruthenium(VI) complexes. Effect of driving force on rate constants
Authors
Issue Date1992
PublisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton
Citation
Journal Of The Chemical Society, Dalton Transactions, 1992 n. 21, p. 3153-3158 How to Cite?
AbstractThe kinetics of alkene oxidation by a series of isostructural trans-dioxoruthenium(VI) complexes with E°(RuVI-RuV) ranging from 0.23 to 0.7 V vs. saturated calomel electrode has been investigated in acetonitrile. The experimental rate law is rate = k2[RuVI][alkene]. A linear free-energy relationship between log k2 and E°(RuVI-RuV) for the oxidation of styrene and norbornene has been observed. Both steric and electronic effects of alkenes as well as the E° of the dioxoruthenium(VI) complexes affect the rate constants. For the oxidation of para-substituted styrenes, a linear Hammett plot of log k2 versus σ+ for the para substituents with a ρ value of -2.1 was found. A charge-transfer mechanism alone is insufficient to explain the experimental findings.
Persistent Identifierhttp://hdl.handle.net/10722/168239
ISSN
2002 Impact Factor: 3.023
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorChe, CMen_US
dc.contributor.authorLi, Cen_US
dc.contributor.authorTang, Wen_US
dc.contributor.authorYu, Wen_US
dc.date.accessioned2012-10-08T03:16:34Z-
dc.date.available2012-10-08T03:16:34Z-
dc.date.issued1992en_US
dc.identifier.citationJournal Of The Chemical Society, Dalton Transactions, 1992 n. 21, p. 3153-3158en_US
dc.identifier.issn1472-7773en_US
dc.identifier.urihttp://hdl.handle.net/10722/168239-
dc.description.abstractThe kinetics of alkene oxidation by a series of isostructural trans-dioxoruthenium(VI) complexes with E°(RuVI-RuV) ranging from 0.23 to 0.7 V vs. saturated calomel electrode has been investigated in acetonitrile. The experimental rate law is rate = k2[RuVI][alkene]. A linear free-energy relationship between log k2 and E°(RuVI-RuV) for the oxidation of styrene and norbornene has been observed. Both steric and electronic effects of alkenes as well as the E° of the dioxoruthenium(VI) complexes affect the rate constants. For the oxidation of para-substituted styrenes, a linear Hammett plot of log k2 versus σ+ for the para substituents with a ρ value of -2.1 was found. A charge-transfer mechanism alone is insufficient to explain the experimental findings.en_US
dc.languageengen_US
dc.publisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/daltonen_US
dc.relation.ispartofJournal of the Chemical Society, Dalton Transactionsen_US
dc.titleKinetics of alkene oxidation by cationic trans-dioxoruthenium(VI) complexes. Effect of driving force on rate constantsen_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.doi10.1039/DT9920003153en_US
dc.identifier.scopuseid_2-s2.0-37049086955en_US
dc.identifier.issue21en_US
dc.identifier.spage3153en_US
dc.identifier.epage3158en_US
dc.identifier.isiWOS:A1992JY10600014-
dc.publisher.placeUnited Kingdomen_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US
dc.identifier.scopusauthoridLi, C=8714186500en_US
dc.identifier.scopusauthoridTang, W=15121154000en_US
dc.identifier.scopusauthoridYu, W=7403913673en_US

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