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Article: Synthesis, structural characterization and reactivities of hexaosmium carbonyl clusters with six-membered cyclic thioether and thioxane ligands

TitleSynthesis, structural characterization and reactivities of hexaosmium carbonyl clusters with six-membered cyclic thioether and thioxane ligands
Authors
Issue Date1999
PublisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/dalton
Citation
Journal of the Chemical Society Dalton Transactions, 1999, n. 12, p. 2077-2086 How to Cite?
AbstractCluster complexes [Os 6(CO) 15{S(CH 2) 4CH 2} {μ-S(CH 2) 4CH 2}] 1 and [Os 5(CO) 15{S(CH 2) 4CH 2}] 2 were isolated from the reaction of [Os 6(CO) 16(MeCN) 2] with S(CH 2) 4CH 2 (L 1) in 24 and 22% yields respectively. Cluster degradation from 1 to 2 can be achieved by addition of a stoichiometric quantity of L 1 in CHCl 3 under reflux. Monosubstituted cluster complex [Os 6(CO) 16{μ-S(CH 2) 3SCH 2}] 3 containing a S(CH 2) 3SCH 2 (L 2) ligand bridging across an Os-Os edge via one of the sulfur atoms was isolated in good yield from a similar reaction. However, similar reaction between [Os 6(CO) 16(MeCN) 2] and S(CH 2) 2SCH 2CH 2 (L 3) gave [Os 6(CO) 16{S(CH 2) 2SCH 2CH 2} 2] 4 as the major product instead. The two thio ligands are found to co-ordinate in terminal fashion to two different vertices of the Os 6 core. Interaction of tridentate sulfur donor ligand SCH 2SCH 2SCH 2 (L 4) with [Os 6(CO) 16(MeCN) 2] afforded [Os 6(CO) 14-(μ-CO)(SCH 2SCH 2SCH 2)] 5 in which the ligand L 4 was found to cap over a triangular face of the Os 6 skeleton. Treatment of mixed-donor ligand S(CH 2) 2OCH 2CH 2 (L 5) yielded a pair of isomeric complexes [Os 6(CO) 15-{(S(CH 2) 2OCH 2CH 2} {μ-S(CH 2) 2OCH 2CH 2}] 6 and [Os 6(CO) 15{O(CH 2) 2SCH 2CH 2) {μ-S(CH 2) 2OCH 2CH 2}] 7. Carboxylation of 6 gave [Os 6(CO) 16{μ-S(CH 2) 2OCH 2CH 2}] 8 and [Os 6(CO) 18]. Hydrogenation of 6 led to the formation of dihydrido cluster [Os 6(CQ) 15(μ-H) 2{S(CH 2) 2OCH 2CH 2} {μ-S(CH 2) 2OCH 2CH 2}] 9. The metal skeleton of 9 can be described as two fused tetrahedra sharing a common edge. All new compounds were fully characterized by spectroscopic and analytical techniques. In addition the structures of 1, 2, 3, 4, 5, 6, 8 and 9 were established by X-ray crystallography.
Persistent Identifierhttp://hdl.handle.net/10722/69461
ISSN
2002 Impact Factor: 3.023
ISI Accession Number ID

 

DC FieldValueLanguage
dc.contributor.authoreid_2-s2.0-33748483048en_HK
dc.contributor.authorWong, WTen_HK
dc.date.accessioned2010-09-06T06:13:52Z-
dc.date.available2010-09-06T06:13:52Z-
dc.date.issued1999en_HK
dc.identifier.citationJournal of the Chemical Society Dalton Transactions, 1999, n. 12, p. 2077-2086en_HK
dc.identifier.issn1472-7773en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69461-
dc.description.abstractCluster complexes [Os 6(CO) 15{S(CH 2) 4CH 2} {μ-S(CH 2) 4CH 2}] 1 and [Os 5(CO) 15{S(CH 2) 4CH 2}] 2 were isolated from the reaction of [Os 6(CO) 16(MeCN) 2] with S(CH 2) 4CH 2 (L 1) in 24 and 22% yields respectively. Cluster degradation from 1 to 2 can be achieved by addition of a stoichiometric quantity of L 1 in CHCl 3 under reflux. Monosubstituted cluster complex [Os 6(CO) 16{μ-S(CH 2) 3SCH 2}] 3 containing a S(CH 2) 3SCH 2 (L 2) ligand bridging across an Os-Os edge via one of the sulfur atoms was isolated in good yield from a similar reaction. However, similar reaction between [Os 6(CO) 16(MeCN) 2] and S(CH 2) 2SCH 2CH 2 (L 3) gave [Os 6(CO) 16{S(CH 2) 2SCH 2CH 2} 2] 4 as the major product instead. The two thio ligands are found to co-ordinate in terminal fashion to two different vertices of the Os 6 core. Interaction of tridentate sulfur donor ligand SCH 2SCH 2SCH 2 (L 4) with [Os 6(CO) 16(MeCN) 2] afforded [Os 6(CO) 14-(μ-CO)(SCH 2SCH 2SCH 2)] 5 in which the ligand L 4 was found to cap over a triangular face of the Os 6 skeleton. Treatment of mixed-donor ligand S(CH 2) 2OCH 2CH 2 (L 5) yielded a pair of isomeric complexes [Os 6(CO) 15-{(S(CH 2) 2OCH 2CH 2} {μ-S(CH 2) 2OCH 2CH 2}] 6 and [Os 6(CO) 15{O(CH 2) 2SCH 2CH 2) {μ-S(CH 2) 2OCH 2CH 2}] 7. Carboxylation of 6 gave [Os 6(CO) 16{μ-S(CH 2) 2OCH 2CH 2}] 8 and [Os 6(CO) 18]. Hydrogenation of 6 led to the formation of dihydrido cluster [Os 6(CQ) 15(μ-H) 2{S(CH 2) 2OCH 2CH 2} {μ-S(CH 2) 2OCH 2CH 2}] 9. The metal skeleton of 9 can be described as two fused tetrahedra sharing a common edge. All new compounds were fully characterized by spectroscopic and analytical techniques. In addition the structures of 1, 2, 3, 4, 5, 6, 8 and 9 were established by X-ray crystallography.-
dc.languageengen_HK
dc.publisherRoyal Society of Chemistry. The Journal's web site is located at http://www.rsc.org/daltonen_HK
dc.relation.ispartofJournal of the Chemical Society Dalton Transactionsen_HK
dc.titleSynthesis, structural characterization and reactivities of hexaosmium carbonyl clusters with six-membered cyclic thioether and thioxane ligandsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1472-7773&volume=&spage=2077&epage=2086&date=1999&atitle=Synthesis,+structural+characterization+and+reactivies+of+hexaosmium+carbonyl+clusters+with+six-membered+cyclic+thioether+and+thioxane+ligandsen_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.identifier.doi10.1039/A900808J-
dc.identifier.scopuseid_2-s2.0-33748483048-
dc.identifier.hkuros45542en_HK
dc.identifier.issue12-
dc.identifier.spage2077-
dc.identifier.epage2086-
dc.identifier.isiWOS:000081308300030-
dc.publisher.placeUnited Kingdom-

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