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Article: Electronic and kinetic isotope effects on the electrooxidation of benzyl alcohols by a monoxo ruthenium (V) complex of tetramethylcyclam

TitleElectronic and kinetic isotope effects on the electrooxidation of benzyl alcohols by a monoxo ruthenium (V) complex of tetramethylcyclam
Authors
KeywordsBenzyl Alcohol
Electrooxidation
Kinetics
Ruthenium
Issue Date1994
Citation
Journal Of Molecular Catalysis, 1994, v. 89 n. 1-2, p. 57-62 How to Cite?
AbstractThe electrooxidation of substituted benzyl alcohols by trans-[Ruv(TMC)(O)(NCO)]2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) was studied in acetonitrile by rotating disc voltammetry. The second order rate constant between RuVO and the benzyl alcohols increases in the presence of electron donating substituents and decreases in the presence of electron withdrawing groups. A linear Hammett plot with a slope of -2.0 was obtained. The large negative reaction constant is consistent with a build up of positive charge at the alcohol in the transition state. The primary kinetic isotope effect (kH/kD) in benzy] alcohol oxidation was determined to be 4.1. The results are consistent with a mechanism involving hydrogen atom abstraction by the oxo ligand on the ruthenium complex. © 1994.
Persistent Identifierhttp://hdl.handle.net/10722/167523
ISSN
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorLee, WOen_US
dc.contributor.authorChe, CMen_US
dc.contributor.authorWong, KYen_US
dc.date.accessioned2012-10-08T03:08:03Z-
dc.date.available2012-10-08T03:08:03Z-
dc.date.issued1994en_US
dc.identifier.citationJournal Of Molecular Catalysis, 1994, v. 89 n. 1-2, p. 57-62en_US
dc.identifier.issn0304-5102en_US
dc.identifier.urihttp://hdl.handle.net/10722/167523-
dc.description.abstractThe electrooxidation of substituted benzyl alcohols by trans-[Ruv(TMC)(O)(NCO)]2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) was studied in acetonitrile by rotating disc voltammetry. The second order rate constant between RuVO and the benzyl alcohols increases in the presence of electron donating substituents and decreases in the presence of electron withdrawing groups. A linear Hammett plot with a slope of -2.0 was obtained. The large negative reaction constant is consistent with a build up of positive charge at the alcohol in the transition state. The primary kinetic isotope effect (kH/kD) in benzy] alcohol oxidation was determined to be 4.1. The results are consistent with a mechanism involving hydrogen atom abstraction by the oxo ligand on the ruthenium complex. © 1994.en_US
dc.languageengen_US
dc.relation.ispartofJournal of Molecular Catalysisen_US
dc.subjectBenzyl Alcoholen_US
dc.subjectElectrooxidationen_US
dc.subjectKineticsen_US
dc.subjectRutheniumen_US
dc.titleElectronic and kinetic isotope effects on the electrooxidation of benzyl alcohols by a monoxo ruthenium (V) complex of tetramethylcyclamen_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.doi10.1016/0304-5102(93)E0286-P-
dc.identifier.scopuseid_2-s2.0-0028413852en_US
dc.identifier.volume89en_US
dc.identifier.issue1-2en_US
dc.identifier.spage57en_US
dc.identifier.epage62en_US
dc.identifier.isiWOS:A1994NK18700008-
dc.identifier.scopusauthoridLee, WO=7407087172en_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US
dc.identifier.scopusauthoridWong, KY=7404760030en_US

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