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Article: Tetraosmium carbonyl clusters containing µ-NH2 amido ligands: syntheses, crystal structures and reactivities

TitleTetraosmium carbonyl clusters containing µ-NH2 amido ligands: syntheses, crystal structures and reactivities
Authors
KeywordsAdsorption
Chemical bonds
Crystal structure
Osmium compounds
Synthesis (chemical)
Issue Date2003
PublisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton
Citation
Dalton Transactions, 2003, n. 3, p. 398-405 How to Cite?
AbstractTreatment of [Os4(μ-H)4(CO)12] with O-tert-butylhydroxylamine hydrochloride (tBuONH2·HCl) afforded two amino ligand containing osmium clusters [Os4(μ-H)4(CO)11(η1-NH2OtBu)] (1) and [Os4(μ-H)4(CO)11{(μ-H)3Os(CO)2(η1-NH2OtBu)2Cl}] (2) in moderate yields. For the same reaction, in the presence of one equivalent of [Os3(CO)12], the novel heptaosmium carbonyl cluster [{Os4(μ-H)2(CO)11(μ-NH2)}{Os3(μ-H)(CO)11}] (3) was isolated together with 1 and 2. This heptaosmium cluster 3 displays an uncommon metal skeleton, where the tetraosmium tetrahedron and the triosmium triangle are connected by a metal–metal bond. Upon the addition of hydrobromic acid (HBr) to a solution of 1, a pair of geometric isomers, unsupported butterfly [Os4(μ-H)4(CO)11(μ-NH2)Br] (4a) and supported butterfly [Os4(μ-H)4(CO)11(μ-NH2)Br] (4b) clusters were formed. They are the first examples of μ-NH2 amido tetraosmium carbonyl clusters, which serve as good models for the adsorbed nitrogen atoms on a stepped metal surface. Refluxing of 4a in toluene for several hours, afforded a new triosmium μ-NH2 amido cluster [Os3(μ-H)2(CO)9(μ-NH2)Br] (5). Addition of an excess of triphenylcarbenium tetrafluoroborate [Ph3C][BF4] to a solution of 4a in dichloromethane gave another tetrahedral μ-NH2 amido tetraosmium cluster [Os4(μ-H)2(CO)11(μ-NH2)Br] (6) in moderate yield upon elimination of two hydrides.
Persistent Identifierhttp://hdl.handle.net/10722/69279
ISSN
2015 Impact Factor: 4.177
2015 SCImago Journal Rankings: 1.404
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorLi, Yen_HK
dc.contributor.authorWong, WTen_HK
dc.date.accessioned2010-09-06T06:12:12Z-
dc.date.available2010-09-06T06:12:12Z-
dc.date.issued2003en_HK
dc.identifier.citationDalton Transactions, 2003, n. 3, p. 398-405en_HK
dc.identifier.issn1477-9226en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69279-
dc.description.abstractTreatment of [Os4(μ-H)4(CO)12] with O-tert-butylhydroxylamine hydrochloride (tBuONH2·HCl) afforded two amino ligand containing osmium clusters [Os4(μ-H)4(CO)11(η1-NH2OtBu)] (1) and [Os4(μ-H)4(CO)11{(μ-H)3Os(CO)2(η1-NH2OtBu)2Cl}] (2) in moderate yields. For the same reaction, in the presence of one equivalent of [Os3(CO)12], the novel heptaosmium carbonyl cluster [{Os4(μ-H)2(CO)11(μ-NH2)}{Os3(μ-H)(CO)11}] (3) was isolated together with 1 and 2. This heptaosmium cluster 3 displays an uncommon metal skeleton, where the tetraosmium tetrahedron and the triosmium triangle are connected by a metal–metal bond. Upon the addition of hydrobromic acid (HBr) to a solution of 1, a pair of geometric isomers, unsupported butterfly [Os4(μ-H)4(CO)11(μ-NH2)Br] (4a) and supported butterfly [Os4(μ-H)4(CO)11(μ-NH2)Br] (4b) clusters were formed. They are the first examples of μ-NH2 amido tetraosmium carbonyl clusters, which serve as good models for the adsorbed nitrogen atoms on a stepped metal surface. Refluxing of 4a in toluene for several hours, afforded a new triosmium μ-NH2 amido cluster [Os3(μ-H)2(CO)9(μ-NH2)Br] (5). Addition of an excess of triphenylcarbenium tetrafluoroborate [Ph3C][BF4] to a solution of 4a in dichloromethane gave another tetrahedral μ-NH2 amido tetraosmium cluster [Os4(μ-H)2(CO)11(μ-NH2)Br] (6) in moderate yield upon elimination of two hydrides.-
dc.languageengen_HK
dc.publisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/daltonen_HK
dc.relation.ispartofDalton Transactionsen_HK
dc.subjectAdsorption-
dc.subjectChemical bonds-
dc.subjectCrystal structure-
dc.subjectOsmium compounds-
dc.subjectSynthesis (chemical)-
dc.titleTetraosmium carbonyl clusters containing µ-NH2 amido ligands: syntheses, crystal structures and reactivitiesen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1472-7773&volume=&spage=398&epage=405&date=2003&atitle=Tetraosmium+carbonyl+clusters+containing+m-NH2+amido+ligands:+syntheses,+crystal+structures+and+reactivitiesen_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.identifier.doi10.1039/B208321C-
dc.identifier.scopuseid_2-s2.0-0037423559-
dc.identifier.hkuros76346en_HK
dc.identifier.issue3-
dc.identifier.spage398-
dc.identifier.epage405-
dc.identifier.isiWOS:000181341800023-
dc.publisher.placeUnited Kingdom-

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