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Article: Ruthenium-cobalt mixed-metal nitrido and nitrene carbonyl clusters: Structure, reactivity, and 15N NMR spectroscopy

TitleRuthenium-cobalt mixed-metal nitrido and nitrene carbonyl clusters: Structure, reactivity, and 15N NMR spectroscopy
Authors
KeywordsCluster compounds
Cobalt
Electrochemistry
Nitrenes
Nitrides
NMR spectroscopy
Ruthenium
Issue Date2001
PublisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.eurjic.org
Citation
European Journal Of Inorganic Chemistry, 2001 n. 5, p. 1321-1338 How to Cite?
AbstractThe reaction of [Ru3(μ-H)2(CO)9(μ3-NOMe)] (1) with [Cp* Co(CO)2] (Cp* = η5-C5Me5) in refluxing THF afforded the new clusters [Ru3Co(μ-H)(CO)9(η5-C5 Me5)(μ4-N)] (2), [Ru2Co(CO)6(μ3-CO)(η5-C 5Me5)(μ3-NH) (3), [Ru5(μ-H)(CO)9(μ-CO)3(η 5-C5Me5)(μ4-NH)] (4), and [Ru6Co(μ3-H)(CO)8(μ-CO)3 (μ4-η2-CO)(η5-C5Me 5)3(μ4-N)] (5). Clusters 2 and 3 have typical butterfly nitrido and triangular nitrene structures, whilst compound 4 is a novel square-pyramidal pentaruthenium μ4-NH carbonyl cluster with a Cp* ligand transferred from the external mononuclear Co complex. Cluster 4 can also be obtained by the reaction of 1 with pentamethylcyclopentadiene in the presence of 1,3-cyclohexadiene, albeit in low yield. Compound 5 consists of a rare Ru6Co metal framework where a basal Ru-Ru edge of the central Ru4 tetrahedron is capped by a Cp*Co fragment and another edge is bridged by a diruthenium unit. Complex 2 was found to be converted into 3 upon deprotonation with 1,8-diazabicyclo[5.4.0]undec-7-ene, on refluxing with [Cp*Co(CO)2], or on exhaustive electrolysis. Upon thermolysis of 2 with PhC2Ph in n-octane, [Ru3Co(CO)6(μ-CO)2(η5-C 5Me5)(μ4-NH)(μ4-η 2-PhC2Ph)] (6) and [Ru3Co(CO)5(μ-CO)2(η5-C 5Me5){μ4-η3-NC(O)C 2(C4H4)CHCH(Ph)}(μ4-η 2-PhC2Ph)] (7) were obtained in moderate yields. The structures of 6 and 7 both consist of a slightly twisted Ru3Co square base with a quadruply bridging PhC2Ph ligand. Cluster 6 is capped by a μ-NH moiety on the opposite side, while in 7 a CO ligand and an ortho-carbon atom of a Ph group from another PhC2Ph ligand interact with the μ4-N nitrido atom. Molecular orbital calculations have been carried out in order to gain further insight into the electronic structures of these interesting square-planar Ru3Co and Ru4 clusters. The butterfly Ru2Co2 nitrido complex [Ru2Co2(CO)9(η5-C 5Me5)(μ4-N)] (8) was isolated from the reaction of [Ru3Co(CO)12(μ4-N)] with [Cp*Co(CO)2] in refluxing THF as a result of metal exchange of an Ru(CO)3 fragment by a Cp*Co moiety. The redox properties of the compounds described herein have been investigated by means of cyclic voltammetry and controlled potential coulometry. Cluster 6 was shown to be able to tolerate both the addition of two electrons and the removal of one electron without significant structural change. The chemical environments of the nitrogen atoms of these clusters have been investigated by analysis of their 15N NMR chemical shifts.
Persistent Identifierhttp://hdl.handle.net/10722/69829
ISSN
2015 Impact Factor: 2.686
2015 SCImago Journal Rankings: 1.018
References

 

DC FieldValueLanguage
dc.contributor.authorHo, ENMen_HK
dc.contributor.authorLin, Zen_HK
dc.contributor.authorWong, WTen_HK
dc.date.accessioned2010-09-06T06:17:13Z-
dc.date.available2010-09-06T06:17:13Z-
dc.date.issued2001en_HK
dc.identifier.citationEuropean Journal Of Inorganic Chemistry, 2001 n. 5, p. 1321-1338en_HK
dc.identifier.issn1434-1948en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69829-
dc.description.abstractThe reaction of [Ru3(μ-H)2(CO)9(μ3-NOMe)] (1) with [Cp* Co(CO)2] (Cp* = η5-C5Me5) in refluxing THF afforded the new clusters [Ru3Co(μ-H)(CO)9(η5-C5 Me5)(μ4-N)] (2), [Ru2Co(CO)6(μ3-CO)(η5-C 5Me5)(μ3-NH) (3), [Ru5(μ-H)(CO)9(μ-CO)3(η 5-C5Me5)(μ4-NH)] (4), and [Ru6Co(μ3-H)(CO)8(μ-CO)3 (μ4-η2-CO)(η5-C5Me 5)3(μ4-N)] (5). Clusters 2 and 3 have typical butterfly nitrido and triangular nitrene structures, whilst compound 4 is a novel square-pyramidal pentaruthenium μ4-NH carbonyl cluster with a Cp* ligand transferred from the external mononuclear Co complex. Cluster 4 can also be obtained by the reaction of 1 with pentamethylcyclopentadiene in the presence of 1,3-cyclohexadiene, albeit in low yield. Compound 5 consists of a rare Ru6Co metal framework where a basal Ru-Ru edge of the central Ru4 tetrahedron is capped by a Cp*Co fragment and another edge is bridged by a diruthenium unit. Complex 2 was found to be converted into 3 upon deprotonation with 1,8-diazabicyclo[5.4.0]undec-7-ene, on refluxing with [Cp*Co(CO)2], or on exhaustive electrolysis. Upon thermolysis of 2 with PhC2Ph in n-octane, [Ru3Co(CO)6(μ-CO)2(η5-C 5Me5)(μ4-NH)(μ4-η 2-PhC2Ph)] (6) and [Ru3Co(CO)5(μ-CO)2(η5-C 5Me5){μ4-η3-NC(O)C 2(C4H4)CHCH(Ph)}(μ4-η 2-PhC2Ph)] (7) were obtained in moderate yields. The structures of 6 and 7 both consist of a slightly twisted Ru3Co square base with a quadruply bridging PhC2Ph ligand. Cluster 6 is capped by a μ-NH moiety on the opposite side, while in 7 a CO ligand and an ortho-carbon atom of a Ph group from another PhC2Ph ligand interact with the μ4-N nitrido atom. Molecular orbital calculations have been carried out in order to gain further insight into the electronic structures of these interesting square-planar Ru3Co and Ru4 clusters. The butterfly Ru2Co2 nitrido complex [Ru2Co2(CO)9(η5-C 5Me5)(μ4-N)] (8) was isolated from the reaction of [Ru3Co(CO)12(μ4-N)] with [Cp*Co(CO)2] in refluxing THF as a result of metal exchange of an Ru(CO)3 fragment by a Cp*Co moiety. The redox properties of the compounds described herein have been investigated by means of cyclic voltammetry and controlled potential coulometry. Cluster 6 was shown to be able to tolerate both the addition of two electrons and the removal of one electron without significant structural change. The chemical environments of the nitrogen atoms of these clusters have been investigated by analysis of their 15N NMR chemical shifts.en_HK
dc.languageengen_HK
dc.publisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.eurjic.orgen_HK
dc.relation.ispartofEuropean Journal of Inorganic Chemistryen_HK
dc.subjectCluster compoundsen_HK
dc.subjectCobalten_HK
dc.subjectElectrochemistryen_HK
dc.subjectNitrenesen_HK
dc.subjectNitridesen_HK
dc.subjectNMR spectroscopyen_HK
dc.subjectRutheniumen_HK
dc.titleRuthenium-cobalt mixed-metal nitrido and nitrene carbonyl clusters: Structure, reactivity, and 15N NMR spectroscopyen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1434-1948&volume=&spage=1321&epage=1338&date=2001&atitle=Ruthenium-Cobalt+Mixed-Metal+Nitrido+and+Nitrene+Carbonyl+Clusters:+Structure,+Reactivity,+and+15N+NMR+Spectroscopyen_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1002/1099-0682(200105)2001:5<1321::AID-EJIC1321>3.0.CO;2-U-
dc.identifier.scopuseid_2-s2.0-0035030640en_HK
dc.identifier.hkuros56707en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0035030640&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.issue5en_HK
dc.identifier.spage1321en_HK
dc.identifier.epage1338en_HK
dc.publisher.placeGermanyen_HK
dc.identifier.scopusauthoridHo, ENM=7102724598en_HK
dc.identifier.scopusauthoridLin, Z=7404230177en_HK
dc.identifier.scopusauthoridWong, WT=7403973084en_HK

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