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Article: The first example of tetraosmium carbonyl clusters containing (m3-NH) nitrene ligands: syntheses and crystal structures

TitleThe first example of tetraosmium carbonyl clusters containing (m3-NH) nitrene ligands: syntheses and crystal structures
Authors
Issue Date2003
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics
Citation
Organometallics, 2003, v. 22 n. 5, p. 1029-1037 How to Cite?
AbstractThe reaction of [Os4(μ-H)4(CO)12] with o-tert-butylhydroxylamine hydrochloride (tBuONH2·HCl) in the presence of trimethylamine-N-oxide (Me3NO) in dichloromethane afforded [Os4(μ-H)4(CO)11{η1-NH2OtBu}] (1) in high yield. Upon the addition of tetrafluoroboric acid (HBF4) into the solution of 1 in acetonitrile, the novel cationic cluster [Os4(μ-H)4(CO)11(μ-NH2)(NCMe)][BF4] (2) formed. Reaction of 1 with HBF4 in the presence of diphenylacetylene gave two geometric isomers, [Os4(μ-H)2(CO)11(μ-NH2){μ-η3-Ph(CHC)Ph}] (3) and [Os4(μ-H)2(CO)11(μ-NH2)(η1-Ph(CHC)Ph)] (4). Treatment of 2 with excess Me3NO in acetonitrile gave [Os4(μ-H)4(CO)10(μ-NH2)(NCMe)2][BF4] (5). The carbonylation of 2 in the refluxing chloroform afforded the neutral clusters [Os3(μ-H)2(CO)9(μ-NH2)Cl] (6) and [Os4(μ-H)3(CO)12(μ-NH2)] (7). Protonation of 7 with trifluoromethylsulfonic acid, CF3SO3H, gave another cationic cluster, [Os4(μ-H)4(CO)12(μ-NH2)][CF3SO3] (8), which is an analogue of 2. Refluxing of 7 in toluene under an argon atmosphere afforded [Os4(μ-H)2(CO)12(μ3-NH)] (9), which is the first example of (μ3-NH) nitrene ligands containing tetraosmium carbonyl clusters. The solid-state structures of 2−9 were established by X-ray analysis. The 1H NMR properties of these clusters were studied, and a correlation between the chemical shift and the structural geometry was established.
Persistent Identifierhttp://hdl.handle.net/10722/69296
ISSN
2015 Impact Factor: 4.186
2015 SCImago Journal Rankings: 2.043
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorLi, Yen_HK
dc.contributor.authorWong, WTen_HK
dc.contributor.authorLin, ZYen_HK
dc.date.accessioned2010-09-06T06:12:21Z-
dc.date.available2010-09-06T06:12:21Z-
dc.date.issued2003en_HK
dc.identifier.citationOrganometallics, 2003, v. 22 n. 5, p. 1029-1037en_HK
dc.identifier.issn0276-7333en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69296-
dc.description.abstractThe reaction of [Os4(μ-H)4(CO)12] with o-tert-butylhydroxylamine hydrochloride (tBuONH2·HCl) in the presence of trimethylamine-N-oxide (Me3NO) in dichloromethane afforded [Os4(μ-H)4(CO)11{η1-NH2OtBu}] (1) in high yield. Upon the addition of tetrafluoroboric acid (HBF4) into the solution of 1 in acetonitrile, the novel cationic cluster [Os4(μ-H)4(CO)11(μ-NH2)(NCMe)][BF4] (2) formed. Reaction of 1 with HBF4 in the presence of diphenylacetylene gave two geometric isomers, [Os4(μ-H)2(CO)11(μ-NH2){μ-η3-Ph(CHC)Ph}] (3) and [Os4(μ-H)2(CO)11(μ-NH2)(η1-Ph(CHC)Ph)] (4). Treatment of 2 with excess Me3NO in acetonitrile gave [Os4(μ-H)4(CO)10(μ-NH2)(NCMe)2][BF4] (5). The carbonylation of 2 in the refluxing chloroform afforded the neutral clusters [Os3(μ-H)2(CO)9(μ-NH2)Cl] (6) and [Os4(μ-H)3(CO)12(μ-NH2)] (7). Protonation of 7 with trifluoromethylsulfonic acid, CF3SO3H, gave another cationic cluster, [Os4(μ-H)4(CO)12(μ-NH2)][CF3SO3] (8), which is an analogue of 2. Refluxing of 7 in toluene under an argon atmosphere afforded [Os4(μ-H)2(CO)12(μ3-NH)] (9), which is the first example of (μ3-NH) nitrene ligands containing tetraosmium carbonyl clusters. The solid-state structures of 2−9 were established by X-ray analysis. The 1H NMR properties of these clusters were studied, and a correlation between the chemical shift and the structural geometry was established.-
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallicsen_HK
dc.relation.ispartofOrganometallicsen_HK
dc.titleThe first example of tetraosmium carbonyl clusters containing (m3-NH) nitrene ligands: syntheses and crystal structuresen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0276-7333&volume=22&spage=1029&epage=1037&date=2003&atitle=The+first+example+of+tetraosmium+carbonyl+clusters+containing+(m3-NH)+nitrene+ligands:++syntheses+and+crystal+structuresen_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.identifier.doi10.1021/om020767v-
dc.identifier.hkuros76341en_HK
dc.identifier.issue5-
dc.identifier.isiWOS:000181208100020-

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