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Article: A novel monooxoruthenium(V) complex containing a polydentate pyridyl amine ligand. Syntheses, reactivities, and X-ray crystal structure of [RuIII(N4O)(H2O)](ClO4)2

TitleA novel monooxoruthenium(V) complex containing a polydentate pyridyl amine ligand. Syntheses, reactivities, and X-ray crystal structure of [RuIII(N4O)(H2O)](ClO4)2
Authors
Issue Date1990
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, 1990, v. 112 n. 6, p. 2284-2291 How to Cite?
AbstractThe syntheses and characterization of cis-[RuIII(tepa)Cl2]+, [RuIII(N4O)(H2O)]2+, and [RuV(N4O)O]2+ complexes are described [tepa = tris(2-(2-pyridyl)ethyl)amine, N4OH = bis(2-(2-pyridyl)ethyl)(2-hydroxy-2-(2-pyridyl)ethyl)amine]. The molar magnetic susceptibilities for [RuIII(N4O)(H2O)]2+ and [RuV(N4O)O]2+ complexes are 1.79 and 2.2 μB, respectively. The X-ray structure of [RuIII(N4O)(H2O)](ClO4)2 has been determined: [RuIII(C21H23N4O)(H 2O)](ClO4)2, M = 666.43, monoclinic, space group P2/c (no. 13), a = 11.644 (1) Å, b = 11.937 (3) Å, c = 18.856 (6) Å, β = 105.39 (2)°, V = 2527 (1) Å3, Z = 4, Dx = 1.753, Dc = 1.752 g cm-3, μ(Mo Kα) = 8.82 cm-1. The Ru-O(OH2) and Ru-O(N4O) distances are 2.115 (3) and 1.961 (4) Å, respectively. The [RuV(N4O)O]2+ complex shows an intense Ru=O stretch at 872 cm-1 which is absent in the [RuIII(N4O)(H2O)]2+ complex. The Ru(V) state in [RuV(N4O)O]2+ has also been confirmed by spectrophotometric redox titration in 0.1 M HClO4 by using [RuII(NH3)4(bpy)]2+ (bpy = 2,2′-bipyridine) as the redox titrant. A stoichiometry of 1:3 has been obtained. The cyclic voltammograms of both [RuIIIHN4O)(H2O)]2+ and [RuV(N4O)O]2+ complexs show two couples at 0.35 and 1.02 V vs SCE in aqueous medium at pH = 1, assignable to a Ru(III/II) and a Ru(V/III) couple, respectively. At 5.5 > pH > 3.5, the wave for the Ru(V/III) couple splits into two waves, a pH-independent one-electron wave for the Ru(V/IV) couple and a two-proton-one-electron wave with a slope of -117 mV/pH unit for the Ru(IV/III) couple. The Ru(IV) state is found to be thermodynamically unstable with respect to disproportionation into Ru(III) and Ru(V) at pH < 3.5. The [RuV(N4O)O]2+ complex is found to be an active oxidant, capable of oxidizing both activated C-H bonds and the C-H bond of cyclohexane. Studies on the reactions of [RuV(N4O)O]2+ with organic substrates indicated that the Ru(V)=O has a higher affinity for hydrogen atom/hydride abstraction than oxo-transfer reaction to C=C double bond.
Persistent Identifierhttp://hdl.handle.net/10722/167341
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorChe, CMen_US
dc.contributor.authorYam, VWWen_US
dc.contributor.authorMak, TCWen_US
dc.date.accessioned2012-10-08T03:05:51Z-
dc.date.available2012-10-08T03:05:51Z-
dc.date.issued1990en_US
dc.identifier.citationJournal Of The American Chemical Society, 1990, v. 112 n. 6, p. 2284-2291en_US
dc.identifier.issn0002-7863en_US
dc.identifier.urihttp://hdl.handle.net/10722/167341-
dc.description.abstractThe syntheses and characterization of cis-[RuIII(tepa)Cl2]+, [RuIII(N4O)(H2O)]2+, and [RuV(N4O)O]2+ complexes are described [tepa = tris(2-(2-pyridyl)ethyl)amine, N4OH = bis(2-(2-pyridyl)ethyl)(2-hydroxy-2-(2-pyridyl)ethyl)amine]. The molar magnetic susceptibilities for [RuIII(N4O)(H2O)]2+ and [RuV(N4O)O]2+ complexes are 1.79 and 2.2 μB, respectively. The X-ray structure of [RuIII(N4O)(H2O)](ClO4)2 has been determined: [RuIII(C21H23N4O)(H 2O)](ClO4)2, M = 666.43, monoclinic, space group P2/c (no. 13), a = 11.644 (1) Å, b = 11.937 (3) Å, c = 18.856 (6) Å, β = 105.39 (2)°, V = 2527 (1) Å3, Z = 4, Dx = 1.753, Dc = 1.752 g cm-3, μ(Mo Kα) = 8.82 cm-1. The Ru-O(OH2) and Ru-O(N4O) distances are 2.115 (3) and 1.961 (4) Å, respectively. The [RuV(N4O)O]2+ complex shows an intense Ru=O stretch at 872 cm-1 which is absent in the [RuIII(N4O)(H2O)]2+ complex. The Ru(V) state in [RuV(N4O)O]2+ has also been confirmed by spectrophotometric redox titration in 0.1 M HClO4 by using [RuII(NH3)4(bpy)]2+ (bpy = 2,2′-bipyridine) as the redox titrant. A stoichiometry of 1:3 has been obtained. The cyclic voltammograms of both [RuIIIHN4O)(H2O)]2+ and [RuV(N4O)O]2+ complexs show two couples at 0.35 and 1.02 V vs SCE in aqueous medium at pH = 1, assignable to a Ru(III/II) and a Ru(V/III) couple, respectively. At 5.5 > pH > 3.5, the wave for the Ru(V/III) couple splits into two waves, a pH-independent one-electron wave for the Ru(V/IV) couple and a two-proton-one-electron wave with a slope of -117 mV/pH unit for the Ru(IV/III) couple. The Ru(IV) state is found to be thermodynamically unstable with respect to disproportionation into Ru(III) and Ru(V) at pH < 3.5. The [RuV(N4O)O]2+ complex is found to be an active oxidant, capable of oxidizing both activated C-H bonds and the C-H bond of cyclohexane. Studies on the reactions of [RuV(N4O)O]2+ with organic substrates indicated that the Ru(V)=O has a higher affinity for hydrogen atom/hydride abstraction than oxo-transfer reaction to C=C double bond.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.titleA novel monooxoruthenium(V) complex containing a polydentate pyridyl amine ligand. Syntheses, reactivities, and X-ray crystal structure of [RuIII(N4O)(H2O)](ClO4)2en_US
dc.typeArticleen_US
dc.identifier.emailChe, CM:cmche@hku.hken_US
dc.identifier.emailYam, VWW:wwyam@hku.hken_US
dc.identifier.authorityChe, CM=rp00670en_US
dc.identifier.authorityYam, VWW=rp00822en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ja00162a032-
dc.identifier.scopuseid_2-s2.0-0001369285en_US
dc.identifier.volume112en_US
dc.identifier.issue6en_US
dc.identifier.spage2284en_US
dc.identifier.epage2291en_US
dc.identifier.isiWOS:A1990CU14400032-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US
dc.identifier.scopusauthoridYam, VWW=18539304700en_US
dc.identifier.scopusauthoridMak, TCW=7401931058en_US

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