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Article: Synthesis, structural characterization and reactivity of triosmium carbonyl clusters containing oxime ligands

TitleSynthesis, structural characterization and reactivity of triosmium carbonyl clusters containing oxime ligands
Authors
Issue Date2002
PublisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/njc
Citation
New Journal Of Chemistry, 2002, v. 26 n. 1, p. 94-104 How to Cite?
AbstractReaction of [Os3(CO)11(NCMe)] with phenyl 2-pyridyl ketoxime produced the clusters [Os3(CO)8{μ-η3-ON=CPh(NC 5H4)}2] 1 and [Os3H(CO)11{η2-ON=CPh(NC5H 4)}] 2 in 4 and 17% yields, respectively. Oxidative addition of the oximes to the clusters with O-H bond cleavage and the loss of labile acetonitrile groups, and in the case of complex 1 decarbonylation, are observed. Cluster 2 possesses an open linear metal skeleton attached to both the pyridine nitrogen and oximato nitrogen on one terminal Os atom. Heating 2 in refluxing toluene gave [Os3(μ-H)(CO)9{μ-η3-ON=CPh(NC 5H4)}] 3 in 13% yield. Treatment of a CH2Cl2 solution of [Os3(CO)10(NCMe)2] with phenyl 2-pyridyl ketoxime at ambient conditions afforded the bridging oximato clusters 1 and 3 in moderate yields. Cluster 3 and 1 equiv. of phenyl 2-pyridyl ketoxime in refluxing toluene led to conversion to clusters 1 and [Os3(CO)8{μ-η3-ON=CPh(NC5 H4)} {μ-η2-N(H)CHPh(NC5H4)}] 4 in 12 and 16% yields, respectively. In cluster 4, one of the oximato moieties is deoxygenated with N-O bond cleavage. Treatment of another oxime ligand, benzophenone oxime, with [Os3(CO)10(NCMe)2] gave [Os3(μ-H)(CO)10{μ-η2-ON=CPh 2}] 5 in moderate yield. On thermolysis of 5 in toluene, [Os3(μ-H)2(CO)9-{μ-η3- ON=CPh(C6H4)}] 6 and [Os3(CO)10(μ-OH){μ-N=CPh2}] 7 were isolated in 27 and 21% yields, respectively. The oxime ligand in 6 is converted to a tridentate ligand. In addition to the μ-η2-oximato N-O bridge, the phenyl carbon on the ligand coordinates to the cluster core by ortho-metallation. Cluster 5 isomerizes thermally to 7, which is formed by oxidative addition of the oxime with N-O bond cleavage. A μ4-oxo hexaosmium cluster, [Os6(CO)16(μ4-O){μ-η3- N=CPh(C6H4)}2] 8, was isolated in low yield upon refluxing 5 in octane. Vacuum pyrolysis of 5 in 140°C yielded a pentaosmium carbonyl cluster, [Os5(CO)15{μ-η3-N=CPh(C6H 4)}] 9. All these clusters have been fully characterized by both spectroscopic and crystallographic techniques.
Persistent Identifierhttp://hdl.handle.net/10722/69629
ISSN
2015 Impact Factor: 3.277
2015 SCImago Journal Rankings: 0.987
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorWong, JSYen_HK
dc.contributor.authorWong, WTen_HK
dc.date.accessioned2010-09-06T06:15:24Z-
dc.date.available2010-09-06T06:15:24Z-
dc.date.issued2002en_HK
dc.identifier.citationNew Journal Of Chemistry, 2002, v. 26 n. 1, p. 94-104en_HK
dc.identifier.issn1144-0546en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69629-
dc.description.abstractReaction of [Os3(CO)11(NCMe)] with phenyl 2-pyridyl ketoxime produced the clusters [Os3(CO)8{μ-η3-ON=CPh(NC 5H4)}2] 1 and [Os3H(CO)11{η2-ON=CPh(NC5H 4)}] 2 in 4 and 17% yields, respectively. Oxidative addition of the oximes to the clusters with O-H bond cleavage and the loss of labile acetonitrile groups, and in the case of complex 1 decarbonylation, are observed. Cluster 2 possesses an open linear metal skeleton attached to both the pyridine nitrogen and oximato nitrogen on one terminal Os atom. Heating 2 in refluxing toluene gave [Os3(μ-H)(CO)9{μ-η3-ON=CPh(NC 5H4)}] 3 in 13% yield. Treatment of a CH2Cl2 solution of [Os3(CO)10(NCMe)2] with phenyl 2-pyridyl ketoxime at ambient conditions afforded the bridging oximato clusters 1 and 3 in moderate yields. Cluster 3 and 1 equiv. of phenyl 2-pyridyl ketoxime in refluxing toluene led to conversion to clusters 1 and [Os3(CO)8{μ-η3-ON=CPh(NC5 H4)} {μ-η2-N(H)CHPh(NC5H4)}] 4 in 12 and 16% yields, respectively. In cluster 4, one of the oximato moieties is deoxygenated with N-O bond cleavage. Treatment of another oxime ligand, benzophenone oxime, with [Os3(CO)10(NCMe)2] gave [Os3(μ-H)(CO)10{μ-η2-ON=CPh 2}] 5 in moderate yield. On thermolysis of 5 in toluene, [Os3(μ-H)2(CO)9-{μ-η3- ON=CPh(C6H4)}] 6 and [Os3(CO)10(μ-OH){μ-N=CPh2}] 7 were isolated in 27 and 21% yields, respectively. The oxime ligand in 6 is converted to a tridentate ligand. In addition to the μ-η2-oximato N-O bridge, the phenyl carbon on the ligand coordinates to the cluster core by ortho-metallation. Cluster 5 isomerizes thermally to 7, which is formed by oxidative addition of the oxime with N-O bond cleavage. A μ4-oxo hexaosmium cluster, [Os6(CO)16(μ4-O){μ-η3- N=CPh(C6H4)}2] 8, was isolated in low yield upon refluxing 5 in octane. Vacuum pyrolysis of 5 in 140°C yielded a pentaosmium carbonyl cluster, [Os5(CO)15{μ-η3-N=CPh(C6H 4)}] 9. All these clusters have been fully characterized by both spectroscopic and crystallographic techniques.en_HK
dc.languageengen_HK
dc.publisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/njcen_HK
dc.relation.ispartofNew Journal of Chemistryen_HK
dc.titleSynthesis, structural characterization and reactivity of triosmium carbonyl clusters containing oxime ligandsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1144-0546&volume=26&spage=94&epage=104&date=2002&atitle=Synthesis,+structural+characterization+and+reactivity+of+triosmium+carbonyl+clusters+containing+oxime+ligandsen_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1039/b107628ken_HK
dc.identifier.scopuseid_2-s2.0-0036169502en_HK
dc.identifier.hkuros68285en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0036169502&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume26en_HK
dc.identifier.issue1en_HK
dc.identifier.spage94en_HK
dc.identifier.epage104en_HK
dc.identifier.isiWOS:000173477400018-
dc.publisher.placeUnited Kingdomen_HK
dc.identifier.scopusauthoridWong, JSY=36771977400en_HK
dc.identifier.scopusauthoridWong, WT=7403973084en_HK

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