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Article: Alkyne oxidations by cis-dioxoruthenium(VI) complexes. A formal [3 + 2] cycloaddition reaction of alkynes with cis-[(Cn*)(CF3CO2)Ru(VI)O2]ClO4 (Cn* = 1,4,7-trimethyl-1,4,7-triazacyclononane)

TitleAlkyne oxidations by cis-dioxoruthenium(VI) complexes. A formal [3 + 2] cycloaddition reaction of alkynes with cis-[(Cn*)(CF3CO2)Ru(VI)O2]ClO4 (Cn* = 1,4,7-trimethyl-1,4,7-triazacyclononane)
Authors
Issue Date2000
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, 2000, v. 122 n. 46, p. 11380-11392 How to Cite?
Abstractcis-Dioxoruthenium(VI) complexes, [Cn*(CF3CO 2)Ru(VI)O2]ClO4 (1) (Cn* = 1,4,7-trimethyl-1,4,7-triazacyclononane) and cis-[(Tet-Me6)Ru(VI)O2](ClO 4)2 (2) (Tet-Me6 = N,N,N',N'-tetramethyl-3,6-dimethyl-3,6-diazaoctane-1,8-diamine), oxidize disubstituted alkynes to 1,2-diketones selectively in good to excellent yields under ambient conditions. The reactions proceed via the formation of dark blue [(Cn*)(CF3CO2)Ru(IV)OC2R1R2O] + intermediates, which display a characteristic UV-visible absorption band at 550-680 nm. With bis(trimethylsilyl)acetylene as substrate and 1 as the oxidant, the intermediate was isolated and structurally characterized by X-ray crystallography as a [3 + 2] cycloadduct. The kinetics of the cycloaddition of 1 with various substituted trimethylsilylacetylenes has been studied by stopped-flow spectrophotometry. With the exception of bis(trimethylsilyl)acetylene, the second-order rate constants were found to vary over a range of less than an order of magnitude irrespective of a 2.3 eV change of the calculated I(p) of the alkynes; therefore, a rate-limiting single electron-transfer mechanism is unlikely. The participation of oxirene (oxene insertion) and metallaoxetene ([2 + 2] cycloaddition) intermediates appears to be implausible based on product analysis. A linear Hammett correlation was established using σ + and σ(jj). parameters for the cycloaddition of 1 with para-substituted aryl trimethylsilylacetylenes, and the rate-limiting vinyl radical intermediate formation is proposed.
Persistent Identifierhttp://hdl.handle.net/10722/167667
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorChe, CMen_US
dc.contributor.authorYu, WYen_US
dc.contributor.authorChan, PMen_US
dc.contributor.authorCheng, WCen_US
dc.contributor.authorPeng, SMen_US
dc.contributor.authorLau, KCen_US
dc.contributor.authorLi, WKen_US
dc.date.accessioned2012-10-08T03:09:41Z-
dc.date.available2012-10-08T03:09:41Z-
dc.date.issued2000en_US
dc.identifier.citationJournal Of The American Chemical Society, 2000, v. 122 n. 46, p. 11380-11392en_US
dc.identifier.issn0002-7863en_US
dc.identifier.urihttp://hdl.handle.net/10722/167667-
dc.description.abstractcis-Dioxoruthenium(VI) complexes, [Cn*(CF3CO 2)Ru(VI)O2]ClO4 (1) (Cn* = 1,4,7-trimethyl-1,4,7-triazacyclononane) and cis-[(Tet-Me6)Ru(VI)O2](ClO 4)2 (2) (Tet-Me6 = N,N,N',N'-tetramethyl-3,6-dimethyl-3,6-diazaoctane-1,8-diamine), oxidize disubstituted alkynes to 1,2-diketones selectively in good to excellent yields under ambient conditions. The reactions proceed via the formation of dark blue [(Cn*)(CF3CO2)Ru(IV)OC2R1R2O] + intermediates, which display a characteristic UV-visible absorption band at 550-680 nm. With bis(trimethylsilyl)acetylene as substrate and 1 as the oxidant, the intermediate was isolated and structurally characterized by X-ray crystallography as a [3 + 2] cycloadduct. The kinetics of the cycloaddition of 1 with various substituted trimethylsilylacetylenes has been studied by stopped-flow spectrophotometry. With the exception of bis(trimethylsilyl)acetylene, the second-order rate constants were found to vary over a range of less than an order of magnitude irrespective of a 2.3 eV change of the calculated I(p) of the alkynes; therefore, a rate-limiting single electron-transfer mechanism is unlikely. The participation of oxirene (oxene insertion) and metallaoxetene ([2 + 2] cycloaddition) intermediates appears to be implausible based on product analysis. A linear Hammett correlation was established using σ + and σ(jj). parameters for the cycloaddition of 1 with para-substituted aryl trimethylsilylacetylenes, and the rate-limiting vinyl radical intermediate formation is proposed.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.htmlen_US
dc.relation.ispartofJournal of the American Chemical Societyen_US
dc.titleAlkyne oxidations by cis-dioxoruthenium(VI) complexes. A formal [3 + 2] cycloaddition reaction of alkynes with cis-[(Cn*)(CF3CO2)Ru(VI)O2]ClO4 (Cn* = 1,4,7-trimethyl-1,4,7-triazacyclononane)en_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.doi10.1021/ja001707oen_US
dc.identifier.scopuseid_2-s2.0-0034703699en_US
dc.identifier.hkuros62361-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0034703699&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume122en_US
dc.identifier.issue46en_US
dc.identifier.spage11380en_US
dc.identifier.epage11392en_US
dc.identifier.isiWOS:000165600300013-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US
dc.identifier.scopusauthoridYu, WY=7403913673en_US
dc.identifier.scopusauthoridChan, PM=8769337500en_US
dc.identifier.scopusauthoridCheng, WC=7402169293en_US
dc.identifier.scopusauthoridPeng, SM=35464852200en_US
dc.identifier.scopusauthoridLau, KC=55025754200en_US
dc.identifier.scopusauthoridLi, WK=7501792241en_US

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