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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
Title | A novel monooxoruthenium(V) complex containing a polydentate pyridyl amine ligand. Syntheses, reactivities, and X-ray crystal structure of [RuIII(N4O)(H2O)](ClO4)2 |
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Authors | |
Issue Date | 1990 |
Publisher | American 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? |
Abstract | The 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 Identifier | http://hdl.handle.net/10722/167341 |
ISSN | 2023 Impact Factor: 14.4 2023 SCImago Journal Rankings: 5.489 |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Che, CM | en_US |
dc.contributor.author | Yam, VWW | en_US |
dc.contributor.author | Mak, TCW | en_US |
dc.date.accessioned | 2012-10-08T03:05:51Z | - |
dc.date.available | 2012-10-08T03:05:51Z | - |
dc.date.issued | 1990 | en_US |
dc.identifier.citation | Journal Of The American Chemical Society, 1990, v. 112 n. 6, p. 2284-2291 | en_US |
dc.identifier.issn | 0002-7863 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/167341 | - |
dc.description.abstract | The 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.language | eng | en_US |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html | en_US |
dc.relation.ispartof | Journal of the American Chemical Society | en_US |
dc.title | A novel monooxoruthenium(V) complex containing a polydentate pyridyl amine ligand. Syntheses, reactivities, and X-ray crystal structure of [RuIII(N4O)(H2O)](ClO4)2 | en_US |
dc.type | Article | en_US |
dc.identifier.email | Che, CM:cmche@hku.hk | en_US |
dc.identifier.email | Yam, VWW:wwyam@hku.hk | en_US |
dc.identifier.authority | Che, CM=rp00670 | en_US |
dc.identifier.authority | Yam, VWW=rp00822 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1021/ja00162a032 | - |
dc.identifier.scopus | eid_2-s2.0-0001369285 | en_US |
dc.identifier.volume | 112 | en_US |
dc.identifier.issue | 6 | en_US |
dc.identifier.spage | 2284 | en_US |
dc.identifier.epage | 2291 | en_US |
dc.identifier.isi | WOS:A1990CU14400032 | - |
dc.publisher.place | United States | en_US |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_US |
dc.identifier.scopusauthorid | Yam, VWW=18539304700 | en_US |
dc.identifier.scopusauthorid | Mak, TCW=7401931058 | en_US |
dc.identifier.issnl | 0002-7863 | - |