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Article: Mechanism of alcohol oxidation by trans-dioxoruthenium(VI): The effect of driving force on reactivity

TitleMechanism of alcohol oxidation by trans-dioxoruthenium(VI): The effect of driving force on reactivity
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. 9, p. 1551-1556 How to Cite?
AbstractThe effect of driving force on the rate of oxidation of alcohols by trans-[RuVILO2]2+{L1 = (2,2′-bipyridine)2; L2 = N,N′-dimethyl-6,7,8,9,10,11,17,18-octahydro-5H-dibenzo[en][1,4,8,12] dioxadiaza-cyclopentadecine; L3 = N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)propylenediamine; L4 = meso-2,3,7,11,12-pentamethyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17), 13,15-triene; L5 = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane} with E°(RuVI-RuIV) ranging from 0.66 to 1.01 V vs. saturated calomel electrode has been investigated. In most cases the complexes behave as two-electron oxidants being reduced to trans-[RuIVL(O)(H2O)]2+. The rate constants (k2) for alcohol oxidation increase with E° of the ruthenium oxidant. The slopes of the linear free-energy plots of log k2 vs. E° for benzyl alcohol and propan-2-ol are -14.7 and -16.9 V-1 respectively. The oxidation is accompanied by large kinetic α-C-H bond isotope effects and negative ΔS‡ values, suggesting association of Ru=O and the α-C-H bond in the transition state. For trans-[RuVIL2O2]2+ the existence of a linear free-energy relationship between log k2 and the ionization energies of the alcohols and the large negative ρ values in Hammett plots for the oxidation of substituted benzyl alcohols indicate a charge-transfer mechanism. A common mechanism involving either a hydride or hydrogen atom abstraction is proposed.
Persistent Identifierhttp://hdl.handle.net/10722/168164
ISSN
2002 Impact Factor: 3.023
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorChe, CMen_US
dc.contributor.authorTang, WTen_US
dc.contributor.authorLee, WOen_US
dc.contributor.authorWong, KYen_US
dc.contributor.authorLau, TCen_US
dc.date.accessioned2012-10-08T03:15:52Z-
dc.date.available2012-10-08T03:15:52Z-
dc.date.issued1992en_US
dc.identifier.citationJournal Of The Chemical Society, Dalton Transactions, 1992 n. 9, p. 1551-1556en_US
dc.identifier.issn1472-7773en_US
dc.identifier.urihttp://hdl.handle.net/10722/168164-
dc.description.abstractThe effect of driving force on the rate of oxidation of alcohols by trans-[RuVILO2]2+{L1 = (2,2′-bipyridine)2; L2 = N,N′-dimethyl-6,7,8,9,10,11,17,18-octahydro-5H-dibenzo[en][1,4,8,12] dioxadiaza-cyclopentadecine; L3 = N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)propylenediamine; L4 = meso-2,3,7,11,12-pentamethyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17), 13,15-triene; L5 = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane} with E°(RuVI-RuIV) ranging from 0.66 to 1.01 V vs. saturated calomel electrode has been investigated. In most cases the complexes behave as two-electron oxidants being reduced to trans-[RuIVL(O)(H2O)]2+. The rate constants (k2) for alcohol oxidation increase with E° of the ruthenium oxidant. The slopes of the linear free-energy plots of log k2 vs. E° for benzyl alcohol and propan-2-ol are -14.7 and -16.9 V-1 respectively. The oxidation is accompanied by large kinetic α-C-H bond isotope effects and negative ΔS‡ values, suggesting association of Ru=O and the α-C-H bond in the transition state. For trans-[RuVIL2O2]2+ the existence of a linear free-energy relationship between log k2 and the ionization energies of the alcohols and the large negative ρ values in Hammett plots for the oxidation of substituted benzyl alcohols indicate a charge-transfer mechanism. A common mechanism involving either a hydride or hydrogen atom abstraction is proposed.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.titleMechanism of alcohol oxidation by trans-dioxoruthenium(VI): The effect of driving force on reactivityen_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/DT9920001551en_US
dc.identifier.scopuseid_2-s2.0-37049067728en_US
dc.identifier.issue9en_US
dc.identifier.spage1551en_US
dc.identifier.epage1556en_US
dc.identifier.isiWOS:A1992HT70700013-
dc.publisher.placeUnited Kingdomen_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US
dc.identifier.scopusauthoridTang, WT=15121154000en_US
dc.identifier.scopusauthoridLee, WO=7407087172en_US
dc.identifier.scopusauthoridWong, KY=7404760030en_US
dc.identifier.scopusauthoridLau, TC=7102222310en_US

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