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- Publisher Website: 10.1039/DT9920003153
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Article: Kinetics of alkene oxidation by cationic trans-dioxoruthenium(VI) complexes. Effect of driving force on rate constants
Title | Kinetics of alkene oxidation by cationic trans-dioxoruthenium(VI) complexes. Effect of driving force on rate constants |
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Authors | |
Issue Date | 1992 |
Publisher | Royal 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? |
Abstract | The 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 Identifier | http://hdl.handle.net/10722/168239 |
ISSN | |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Che, CM | en_US |
dc.contributor.author | Li, C | en_US |
dc.contributor.author | Tang, W | en_US |
dc.contributor.author | Yu, W | en_US |
dc.date.accessioned | 2012-10-08T03:16:34Z | - |
dc.date.available | 2012-10-08T03:16:34Z | - |
dc.date.issued | 1992 | en_US |
dc.identifier.citation | Journal Of The Chemical Society, Dalton Transactions, 1992 n. 21, p. 3153-3158 | en_US |
dc.identifier.issn | 1472-7773 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/168239 | - |
dc.description.abstract | The 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.language | eng | en_US |
dc.publisher | Royal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton | en_US |
dc.relation.ispartof | Journal of the Chemical Society, Dalton Transactions | en_US |
dc.title | Kinetics of alkene oxidation by cationic trans-dioxoruthenium(VI) complexes. Effect of driving force on rate constants | en_US |
dc.type | Article | en_US |
dc.identifier.email | Che, CM:cmche@hku.hk | en_US |
dc.identifier.authority | Che, CM=rp00670 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1039/DT9920003153 | en_US |
dc.identifier.scopus | eid_2-s2.0-37049086955 | en_US |
dc.identifier.issue | 21 | en_US |
dc.identifier.spage | 3153 | en_US |
dc.identifier.epage | 3158 | en_US |
dc.identifier.isi | WOS:A1992JY10600014 | - |
dc.publisher.place | United Kingdom | en_US |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_US |
dc.identifier.scopusauthorid | Li, C=8714186500 | en_US |
dc.identifier.scopusauthorid | Tang, W=15121154000 | en_US |
dc.identifier.scopusauthorid | Yu, W=7403913673 | en_US |
dc.identifier.issnl | 1364-5447 | - |