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Article: Imido transfer from bis(imido)ruthenium(VI) porphyrins to hydrocarbons: Effect of imido substituents, C-H bond dissociation energies, and Ru VI/V reduction potentials

TitleImido transfer from bis(imido)ruthenium(VI) porphyrins to hydrocarbons: Effect of imido substituents, C-H bond dissociation energies, and Ru VI/V reduction potentials
Authors
Issue Date2005
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html
Citation
Journal Of The American Chemical Society, 2005, v. 127 n. 47, p. 16629-16640 How to Cite?
Abstract[RuVI(TMP)(NSO2R)2] (SO2R = Ms, Ts, Bs, Cs, Ns; R = p-C6H4OMe, p-C6H 4Me, C6H5, p-C6H4-Cl, p-C6H4NO2, respectively) and [Ru VI(Por)(NTs)2] (Por = 2,6-Cl2TPP, F 20-TPP) were prepared by the reactions of [RuII(Por)(CO)] with Phl=NSO2R in CH2Cl2. These complexes exhibit reversible RuVI/V couple with E1/2 = -0.41 to -0.12 V vs Cp2Fe+/10 and undergo imido transfer reactions with styrenes, norbornene, cis-cyclooctene, indene, ethylbenzenes, cumene, 9,10-dihydroanthracene, xanthene, cyclohexene, toluene, and tetrahydrofuran to afford aziridines or amides in up to 85% yields. The second-order rate constants (k2) of the aziridination/amidation reactions at 298 K were determined to be (2.6 ± 0.1) × 10-5 to 14.4 ± 0.6 dm3 mol-1 s-1, which generally increase with increasing RuVI/V reduction potential of the imido complexes and decreasing C-H bond dissociation energy (BDE) of the hydrocarbons. A linear correlation was observed between log K (K is the k2 value divided by the number of reactive hydrogens) and BDE and between log k2 and E1/2(RuVI/V); the linearity in the former case supports a H-atom abstraction mechanism. The amidation by [RuVI(TMP)(NNs) 2] reverses the thermodynamic reactivity order cumene > ethylbenzene/toluene, with K(3° C-H)/K(2° C-H) = 0.2 and K(3° C-H)/K(1° C-H) = 0.8. © 2005 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/167978
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLeung, SKYen_HK
dc.contributor.authorTsui, WMen_HK
dc.contributor.authorHuang, JSen_HK
dc.contributor.authorChe, CMen_HK
dc.contributor.authorLiang, JLen_HK
dc.contributor.authorZhu, Nen_HK
dc.date.accessioned2012-10-08T03:13:40Z-
dc.date.available2012-10-08T03:13:40Z-
dc.date.issued2005en_HK
dc.identifier.citationJournal Of The American Chemical Society, 2005, v. 127 n. 47, p. 16629-16640en_HK
dc.identifier.issn0002-7863en_HK
dc.identifier.urihttp://hdl.handle.net/10722/167978-
dc.description.abstract[RuVI(TMP)(NSO2R)2] (SO2R = Ms, Ts, Bs, Cs, Ns; R = p-C6H4OMe, p-C6H 4Me, C6H5, p-C6H4-Cl, p-C6H4NO2, respectively) and [Ru VI(Por)(NTs)2] (Por = 2,6-Cl2TPP, F 20-TPP) were prepared by the reactions of [RuII(Por)(CO)] with Phl=NSO2R in CH2Cl2. These complexes exhibit reversible RuVI/V couple with E1/2 = -0.41 to -0.12 V vs Cp2Fe+/10 and undergo imido transfer reactions with styrenes, norbornene, cis-cyclooctene, indene, ethylbenzenes, cumene, 9,10-dihydroanthracene, xanthene, cyclohexene, toluene, and tetrahydrofuran to afford aziridines or amides in up to 85% yields. The second-order rate constants (k2) of the aziridination/amidation reactions at 298 K were determined to be (2.6 ± 0.1) × 10-5 to 14.4 ± 0.6 dm3 mol-1 s-1, which generally increase with increasing RuVI/V reduction potential of the imido complexes and decreasing C-H bond dissociation energy (BDE) of the hydrocarbons. A linear correlation was observed between log K (K is the k2 value divided by the number of reactive hydrogens) and BDE and between log k2 and E1/2(RuVI/V); the linearity in the former case supports a H-atom abstraction mechanism. The amidation by [RuVI(TMP)(NNs) 2] reverses the thermodynamic reactivity order cumene > ethylbenzene/toluene, with K(3° C-H)/K(2° C-H) = 0.2 and K(3° C-H)/K(1° C-H) = 0.8. © 2005 American Chemical Society.en_HK
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.htmlen_HK
dc.relation.ispartofJournal of the American Chemical Societyen_HK
dc.titleImido transfer from bis(imido)ruthenium(VI) porphyrins to hydrocarbons: Effect of imido substituents, C-H bond dissociation energies, and Ru VI/V reduction potentialsen_HK
dc.typeArticleen_HK
dc.identifier.emailHuang, JS: jshuang@hku.hken_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.authorityHuang, JS=rp00709en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ja0542789en_HK
dc.identifier.pmid16305252-
dc.identifier.scopuseid_2-s2.0-28444479526en_HK
dc.identifier.hkuros114267-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-28444479526&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume127en_HK
dc.identifier.issue47en_HK
dc.identifier.spage16629en_HK
dc.identifier.epage16640en_HK
dc.identifier.isiWOS:000233617900063-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridLeung, SKY=36546285500en_HK
dc.identifier.scopusauthoridTsui, WM=36000681700en_HK
dc.identifier.scopusauthoridHuang, JS=7407192639en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK
dc.identifier.scopusauthoridLiang, JL=7404541484en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK

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