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Article: Reactions of the alkylidyne cluster [Os3(μ-H)2(CO)9(μ3-CNC5H4CHCH2)]. Crystal structures of [Os3(μ-H)2(CO)9(μ3-CNC5H4CHCH2)], [Os3(μ-H)2(CO)9(μ3-CNC5H4-μ-η2-CHCH)Os3(μ-H)(CO)10] and [Os3(μ-H)2(CO)9(μ-3-CNC5H4-C(O)CH3)]

TitleReactions of the alkylidyne cluster [Os3(μ-H)2(CO)9(μ3-CNC5H4CHCH2)]. Crystal structures of [Os3(μ-H)2(CO)9(μ3-CNC5H4CHCH2)], [Os3(μ-H)2(CO)9(μ3-CNC5H4-μ-η2-CHCH)Os3(μ-H)(CO)10] and [Os3(μ-H)2(CO)9(μ-3-CNC5H4-C(O)CH3)]
Authors
KeywordsOsmium
Carbonyl
Cluster
Alkylidyne
Solvatochromism
Issue Date1995
PublisherElsevier SA. The Journal's web site is located at http://www.elsevier.com/locate/jorganchem
Citation
Journal of Organometallic Chemistry, 1995, v. 493 Nos1-2, p. 229-237 How to Cite?
AbstractThe neutral triosmium alkylidyne cluster [Os3(μ-H)2(CO)9(μ3-CNC5H4CHCH2)] (1) has been made in good yield by the reaction of [Os3(μ-H)3(CO)9(μ3-CCl)] with one equivalent of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in the presence of an excess of 4-vinylpyridine. The reaction of 1 with [Os3(CO)10(NCMe)2] in refluxing n-hexane affords the linked cluster [Os3(μ-H)2(CO)9(μ3-CNC5H4-μ-η2-CHCHOs3(μ-H)(CO)10] (2) in in moderate yield, while the Wacker-type reaction of 1 with a trace amount of water in the presence of Wilkinson's catalyst RhCl(PPh3)3 in refluxing dichloromethane yields the 4-acetylpyridine derivative of the corresponding alkylidyne cluster [Os3(μ-H)2(CO)9(μ3-CNC5H4C(O)CH3)] (3). The structures of compounds 1–3 have been determined by single crystal X-ray diffraction studies. The structure of 1 involves a triosmium alkylidyne metal core with the 4-vinylpyridine moiety bonded to the μ3-bridging alkylidyne carbon atom. In the case of 2 the triosmium alkylidyne metal core is linked to another triosmium cluster unit via a 4-vinylpyridine moiety, while 3 contains an alkylidyne metal core with the 4-acetylpyridine ligand attached to the apical carbon atom. The M.L.C.T. transitions of all three complexes show strong solvent dependency, displaying unusually large negative solvatochromism in a wide range of organic solvents. This suggests that a less polar excited state is produced by photoexcitation.
Persistent Identifierhttp://hdl.handle.net/10722/70289
ISSN
2015 Impact Factor: 2.336
2015 SCImago Journal Rankings: 0.732
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authorWong, WYen_HK
dc.contributor.authorHu, ZSen_HK
dc.contributor.authorWong, WTen_HK
dc.date.accessioned2010-09-06T06:21:28Z-
dc.date.available2010-09-06T06:21:28Z-
dc.date.issued1995en_HK
dc.identifier.citationJournal of Organometallic Chemistry, 1995, v. 493 Nos1-2, p. 229-237en_HK
dc.identifier.issn0022-328Xen_HK
dc.identifier.urihttp://hdl.handle.net/10722/70289-
dc.description.abstractThe neutral triosmium alkylidyne cluster [Os3(μ-H)2(CO)9(μ3-CNC5H4CHCH2)] (1) has been made in good yield by the reaction of [Os3(μ-H)3(CO)9(μ3-CCl)] with one equivalent of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in the presence of an excess of 4-vinylpyridine. The reaction of 1 with [Os3(CO)10(NCMe)2] in refluxing n-hexane affords the linked cluster [Os3(μ-H)2(CO)9(μ3-CNC5H4-μ-η2-CHCHOs3(μ-H)(CO)10] (2) in in moderate yield, while the Wacker-type reaction of 1 with a trace amount of water in the presence of Wilkinson's catalyst RhCl(PPh3)3 in refluxing dichloromethane yields the 4-acetylpyridine derivative of the corresponding alkylidyne cluster [Os3(μ-H)2(CO)9(μ3-CNC5H4C(O)CH3)] (3). The structures of compounds 1–3 have been determined by single crystal X-ray diffraction studies. The structure of 1 involves a triosmium alkylidyne metal core with the 4-vinylpyridine moiety bonded to the μ3-bridging alkylidyne carbon atom. In the case of 2 the triosmium alkylidyne metal core is linked to another triosmium cluster unit via a 4-vinylpyridine moiety, while 3 contains an alkylidyne metal core with the 4-acetylpyridine ligand attached to the apical carbon atom. The M.L.C.T. transitions of all three complexes show strong solvent dependency, displaying unusually large negative solvatochromism in a wide range of organic solvents. This suggests that a less polar excited state is produced by photoexcitation.-
dc.languageengen_HK
dc.publisherElsevier SA. The Journal's web site is located at http://www.elsevier.com/locate/jorganchemen_HK
dc.relation.ispartofJournal of Organometallic Chemistryen_HK
dc.subjectOsmium-
dc.subjectCarbonyl-
dc.subjectCluster-
dc.subjectAlkylidyne-
dc.subjectSolvatochromism-
dc.titleReactions of the alkylidyne cluster [Os3(μ-H)2(CO)9(μ3-CNC5H4CHCH2)]. Crystal structures of [Os3(μ-H)2(CO)9(μ3-CNC5H4CHCH2)], [Os3(μ-H)2(CO)9(μ3-CNC5H4-μ-η2-CHCH)Os3(μ-H)(CO)10] and [Os3(μ-H)2(CO)9(μ-3-CNC5H4-C(O)CH3)]en_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0022-328X&volume=493 Nos1-2&spage=229&epage=237&date=1995&atitle=Reactions+of+alkylidyne+cluster+[Os3(m-H)2(CO)9(m3-CNC5H4CH=CH2)].+Crystal+structures+of+[Os3(m-H)2(CO)9(m3-CNC5H4CH=CH2)],+[Os3(m-H)2(CO)9(m3-CNC5H4-h2-CH=Cen_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.identifier.doi10.1016/0022-328X(94)05332-6-
dc.identifier.hkuros14546en_HK
dc.identifier.isiWOS:A1995QX75300035-

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