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Article: Synthesis and structural characterisation of ruthenium carbonyl clusters containing hydrocarbyl ligands derived from (hydroxy)alkynes HC≡CC(H)(OH)CH 3

TitleSynthesis and structural characterisation of ruthenium carbonyl clusters containing hydrocarbyl ligands derived from (hydroxy)alkynes HC≡CC(H)(OH)CH 3
Authors
Issue Date1998
Citation
Journal Of The Chemical Society - Dalton Transactions, 1998 n. 20, p. 3391-3396 How to Cite?
AbstractFive new ruthenium ketonic clusters [Ru 4(CO) 12{μ 4-η 1:η 1:η 2:η 2-CH 3C(H)CCC(H)CH 2C(O)CH 3}] 1 (10%), [Ru 5(CO) 14(μ-H) 2{μ 4-η 1:η 1:η 2:η 2-CC(H)C(O)CH 3}] 2 (15%), [Ru 6(CO) 16{μ 4-η 1:η 1:η 2:η 2-CC(H)C(O)CH 3} 2] 3 (15%), [Ru 7(CO) 19{μ 4-η 1:η 1:η 2:η 2-CC(H)C(O)CH 3}{μ 5-η 1:η 1:η 1:η 1:η 2-CCC(H)CH 3}] 4 (8%), and [Ru 5(CO) 12(μ-CO){μ 4-η 1:η 1:η 2:η 2-CC(H)C(O)CH 3}(μ 4-η 2-HCCCH 2CH 3)] 5 (10%) have been synthesised by reaction of but-3-yn-2-ol with triruthenium dodecacarbonyl, in cyclohexane, under reflux. All the compounds have been fully characterised by spectroscopic and X-ray diffraction methods. The structure of 1 is based on a Ru 4 butterfly skeleton containing a fragment of C 8 ketonic chain which arises from the coupling of two ligand molecules with the elimination of a water molecule. An interesting feature in clusters 2, 3, 4 and 5 is the formation of a metallocycloketonic ring with a μ 4-η 1:η 1:η 2:η 2 coordination mode which is derived from the activation of the C≡C triple bond. Both 2 and 5 consist of a wingtip bridged butterfly core, which is also bonded with two bridged hydrides in 2 and a μ 4-η 2 acetylide fragment in 5 respectively. Cluster 2 is also closely related to cluster 3, in that it seems to be a monomeric unit of 3 forming a six atom raft geometry with two metallocycloketonic rings. The metal core of 4 is similar to 3, except that one Ru-Ru bond in 4 is broken to form two more metal-metal bonds with an additional Ru atom to give a novel Ru 7 core, which is best described as a distorted Ru 4 square plane sharing an edge with an edge-bridged butterfly. Moreover, one of the metallocycloketonic rings in 3 is replaced by an allenyl CCC(H)CH 3 ligand, which is coordinated to an edge-bridged butterfly in 4.
Persistent Identifierhttp://hdl.handle.net/10722/91500
ISSN
1999 Impact Factor: 2.31
References

 

DC FieldValueLanguage
dc.contributor.authorLau, CSWen_HK
dc.contributor.authorWong, WTen_HK
dc.date.accessioned2010-09-17T10:20:24Z-
dc.date.available2010-09-17T10:20:24Z-
dc.date.issued1998en_HK
dc.identifier.citationJournal Of The Chemical Society - Dalton Transactions, 1998 n. 20, p. 3391-3396en_HK
dc.identifier.issn0300-9246en_HK
dc.identifier.urihttp://hdl.handle.net/10722/91500-
dc.description.abstractFive new ruthenium ketonic clusters [Ru 4(CO) 12{μ 4-η 1:η 1:η 2:η 2-CH 3C(H)CCC(H)CH 2C(O)CH 3}] 1 (10%), [Ru 5(CO) 14(μ-H) 2{μ 4-η 1:η 1:η 2:η 2-CC(H)C(O)CH 3}] 2 (15%), [Ru 6(CO) 16{μ 4-η 1:η 1:η 2:η 2-CC(H)C(O)CH 3} 2] 3 (15%), [Ru 7(CO) 19{μ 4-η 1:η 1:η 2:η 2-CC(H)C(O)CH 3}{μ 5-η 1:η 1:η 1:η 1:η 2-CCC(H)CH 3}] 4 (8%), and [Ru 5(CO) 12(μ-CO){μ 4-η 1:η 1:η 2:η 2-CC(H)C(O)CH 3}(μ 4-η 2-HCCCH 2CH 3)] 5 (10%) have been synthesised by reaction of but-3-yn-2-ol with triruthenium dodecacarbonyl, in cyclohexane, under reflux. All the compounds have been fully characterised by spectroscopic and X-ray diffraction methods. The structure of 1 is based on a Ru 4 butterfly skeleton containing a fragment of C 8 ketonic chain which arises from the coupling of two ligand molecules with the elimination of a water molecule. An interesting feature in clusters 2, 3, 4 and 5 is the formation of a metallocycloketonic ring with a μ 4-η 1:η 1:η 2:η 2 coordination mode which is derived from the activation of the C≡C triple bond. Both 2 and 5 consist of a wingtip bridged butterfly core, which is also bonded with two bridged hydrides in 2 and a μ 4-η 2 acetylide fragment in 5 respectively. Cluster 2 is also closely related to cluster 3, in that it seems to be a monomeric unit of 3 forming a six atom raft geometry with two metallocycloketonic rings. The metal core of 4 is similar to 3, except that one Ru-Ru bond in 4 is broken to form two more metal-metal bonds with an additional Ru atom to give a novel Ru 7 core, which is best described as a distorted Ru 4 square plane sharing an edge with an edge-bridged butterfly. Moreover, one of the metallocycloketonic rings in 3 is replaced by an allenyl CCC(H)CH 3 ligand, which is coordinated to an edge-bridged butterfly in 4.en_HK
dc.languageengen_HK
dc.relation.ispartofJournal of the Chemical Society - Dalton Transactionsen_HK
dc.titleSynthesis and structural characterisation of ruthenium carbonyl clusters containing hydrocarbyl ligands derived from (hydroxy)alkynes HC≡CC(H)(OH)CH 3en_HK
dc.typeArticleen_HK
dc.identifier.emailLau, CSW: cslau@hku.hken_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityLau, CSW=rp01348en_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1039/A805368E-
dc.identifier.scopuseid_2-s2.0-33748493378en_HK
dc.identifier.hkuros40335-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-33748493378&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.issue20en_HK
dc.identifier.spage3391en_HK
dc.identifier.epage3396en_HK
dc.identifier.scopusauthoridLau, CSW=14035682100en_HK
dc.identifier.scopusauthoridWong, WT=7403973084en_HK

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