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Article: Synthesis, Characterisation, Crystal Structures, Reactivity, and Electrochemistry of Ruthenium-Nitrido, Ruthenium-Cobalt-Imido and Ruthenapyrrolidone Carbonyl Clusters Containing Alkyne Ligands

TitleSynthesis, Characterisation, Crystal Structures, Reactivity, and Electrochemistry of Ruthenium-Nitrido, Ruthenium-Cobalt-Imido and Ruthenapyrrolidone Carbonyl Clusters Containing Alkyne Ligands
Authors
KeywordsChemical binding
Complex formation
Crystal structure
Electrochemistry
Synthesis
Issue Date2001
PublisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry
Citation
Chemistry: A European Journal, 2001, v. 7 n. 1, p. 258-271 How to Cite?
AbstractThermolysis of [Ru3(CO)9(μ3-NOMe)(μ3-η2-PhC2Ph)] (1) with two equivalents of [Cp*Co(CO)2] in THF afforded four new clusters, brown [Ru5(CO)8(μ-CO)3(η5-C5Me5)(μ5-N)(μ4-η2-PhC2Ph)] (2), green [Ru3Co2(CO)7(μ3-CO)(η5-C5Me5)2(μ3-NH){μ4-η8-C6H4C(H)C(Ph)}] (3), orange [Ru3(CO)7(μ-η6-C5Me4CH2){μ-η3-PhC2(Ph)C(O)N(OMe)}] (4) and pale yellow [Ru2(CO)6{μ-η3-PhC2(Ph)C(O)N(OMe)}] (5). Cluster 2 is a pentaruthenium μ5-nitrido complex, in which the five metal atoms are arranged in a novel “spiked” square-planar metal skeleton with a quadruply bridging alkyne ligand. The μ5-nitrido N atom exhibits an unusually low frequency chemical shift in its 15N NMR spectrum. Cluster 3 contains a triangular Ru2Co–imido moiety linked to a ruthenium–cobaltocene through the μ4-η8-C6H4C(H)C(Ph) ligand. Clusters 4 and 5 are both metallapyrrolidone complexes, in which interaction of diphenylacetylene with CO and the NOMe nitrene moiety were observed. In 4, one methyl group of the Cp* ring is activated and interacts with a ruthenium atom. The “distorted” Ru3Co butterfly nitrido complex [Ru3Co(CO)5(η5-C5Me5)(μ4-N)(μ3-η2-PhC2Ph)(μ-I)2I] (6) was isolated from the reaction of 1 with [Cp*Co(CO)I2] heated under reflux in THF, in which a Ru−Ru wing edge is missing. Two bridging and one terminal iodides were found to be placed along the two Ru−Ru wing edges and at a hinge Ru atom, respectively. The redox properties of the selected compounds in this study were investigated by using cyclic voltammetry and controlled potential coulometry. 15N magnetic resonance spectroscopy studies were also performed on these clusters.
Persistent Identifierhttp://hdl.handle.net/10722/68927
ISSN
2015 Impact Factor: 5.771
2015 SCImago Journal Rankings: 2.323

 

DC FieldValueLanguage
dc.contributor.authorHo, ENMen_HK
dc.contributor.authorLin, Zen_HK
dc.contributor.authorWong, WTen_HK
dc.date.accessioned2010-09-06T06:08:59Z-
dc.date.available2010-09-06T06:08:59Z-
dc.date.issued2001en_HK
dc.identifier.citationChemistry: A European Journal, 2001, v. 7 n. 1, p. 258-271en_HK
dc.identifier.issn0947-6539en_HK
dc.identifier.urihttp://hdl.handle.net/10722/68927-
dc.description.abstractThermolysis of [Ru3(CO)9(μ3-NOMe)(μ3-η2-PhC2Ph)] (1) with two equivalents of [Cp*Co(CO)2] in THF afforded four new clusters, brown [Ru5(CO)8(μ-CO)3(η5-C5Me5)(μ5-N)(μ4-η2-PhC2Ph)] (2), green [Ru3Co2(CO)7(μ3-CO)(η5-C5Me5)2(μ3-NH){μ4-η8-C6H4C(H)C(Ph)}] (3), orange [Ru3(CO)7(μ-η6-C5Me4CH2){μ-η3-PhC2(Ph)C(O)N(OMe)}] (4) and pale yellow [Ru2(CO)6{μ-η3-PhC2(Ph)C(O)N(OMe)}] (5). Cluster 2 is a pentaruthenium μ5-nitrido complex, in which the five metal atoms are arranged in a novel “spiked” square-planar metal skeleton with a quadruply bridging alkyne ligand. The μ5-nitrido N atom exhibits an unusually low frequency chemical shift in its 15N NMR spectrum. Cluster 3 contains a triangular Ru2Co–imido moiety linked to a ruthenium–cobaltocene through the μ4-η8-C6H4C(H)C(Ph) ligand. Clusters 4 and 5 are both metallapyrrolidone complexes, in which interaction of diphenylacetylene with CO and the NOMe nitrene moiety were observed. In 4, one methyl group of the Cp* ring is activated and interacts with a ruthenium atom. The “distorted” Ru3Co butterfly nitrido complex [Ru3Co(CO)5(η5-C5Me5)(μ4-N)(μ3-η2-PhC2Ph)(μ-I)2I] (6) was isolated from the reaction of 1 with [Cp*Co(CO)I2] heated under reflux in THF, in which a Ru−Ru wing edge is missing. Two bridging and one terminal iodides were found to be placed along the two Ru−Ru wing edges and at a hinge Ru atom, respectively. The redox properties of the selected compounds in this study were investigated by using cyclic voltammetry and controlled potential coulometry. 15N magnetic resonance spectroscopy studies were also performed on these clusters.-
dc.languageengen_HK
dc.publisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistryen_HK
dc.relation.ispartofChemistry: A European Journalen_HK
dc.subjectChemical binding-
dc.subjectComplex formation-
dc.subjectCrystal structure-
dc.subjectElectrochemistry-
dc.subjectSynthesis-
dc.titleSynthesis, Characterisation, Crystal Structures, Reactivity, and Electrochemistry of Ruthenium-Nitrido, Ruthenium-Cobalt-Imido and Ruthenapyrrolidone Carbonyl Clusters Containing Alkyne Ligandsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0947-6539&volume=7&issue=1&spage=258&epage=271&date=2001&atitle=Synthesis,+Characterization,+Crystal+Structures,+Reactivity,+and+Electrochemistry+of+Ruthenium-Nitrido,+Ruthenium-Coblat-Imido+and+Ruthenapyrrolidone+Carbonyl+Clusters+Containing+Alkyne+Ligandsen_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.identifier.doi10.1002/1521-3765(20010105)7:1<258::AID-CHEM258>3.0.CO;2-I-
dc.identifier.scopuseid_2-s2.0-0035808228-
dc.identifier.hkuros56702en_HK
dc.identifier.volume7-
dc.identifier.issue1-
dc.identifier.spage258-
dc.identifier.epage271-
dc.publisher.placeGermany-

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