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Article: The first example of tetraosmium carbonyl clusters containing (m3-NH) nitrene ligands: syntheses and crystal structures
Title | The first example of tetraosmium carbonyl clusters containing (m3-NH) nitrene ligands: syntheses and crystal structures |
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Authors | |
Issue Date | 2003 |
Publisher | American 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? |
Abstract | The 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 Identifier | http://hdl.handle.net/10722/69296 |
ISSN | 2023 Impact Factor: 2.5 2023 SCImago Journal Rankings: 0.654 |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Li, Y | en_HK |
dc.contributor.author | Wong, WT | en_HK |
dc.contributor.author | Lin, ZY | en_HK |
dc.date.accessioned | 2010-09-06T06:12:21Z | - |
dc.date.available | 2010-09-06T06:12:21Z | - |
dc.date.issued | 2003 | en_HK |
dc.identifier.citation | Organometallics, 2003, v. 22 n. 5, p. 1029-1037 | en_HK |
dc.identifier.issn | 0276-7333 | en_HK |
dc.identifier.uri | http://hdl.handle.net/10722/69296 | - |
dc.description.abstract | The 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.language | eng | en_HK |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/organometallics | en_HK |
dc.relation.ispartof | Organometallics | en_HK |
dc.title | The first example of tetraosmium carbonyl clusters containing (m3-NH) nitrene ligands: syntheses and crystal structures | en_HK |
dc.type | Article | en_HK |
dc.identifier.openurl | http://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+structures | en_HK |
dc.identifier.email | Wong, WT: wtwong@hku.hk | en_HK |
dc.identifier.authority | Wong, WT=rp00811 | en_HK |
dc.identifier.doi | 10.1021/om020767v | - |
dc.identifier.scopus | eid_2-s2.0-0037416247 | - |
dc.identifier.hkuros | 76341 | en_HK |
dc.identifier.issue | 5 | - |
dc.identifier.isi | WOS:000181208100020 | - |
dc.identifier.issnl | 0276-7333 | - |