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Article: Synthesis and structural characterisation of ruthenium carbonyl clusters containing hydrocarbyl ligands derived from (hydroxy)alkynes HC≡CC(H)(OH)CH3
Title | Synthesis and structural characterisation of ruthenium carbonyl clusters containing hydrocarbyl ligands derived from (hydroxy)alkynes HC≡CC(H)(OH)CH3 |
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Authors | |
Issue Date | 1998 |
Citation | Journal of the Chemical Society - Dalton Transactions, 1998 n. 20, p. 3391-3396 How to Cite? |
Abstract | Five 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 Identifier | http://hdl.handle.net/10722/91500 |
ISSN | |
References |
DC Field | Value | Language |
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dc.contributor.author | Lau, CSW | en_HK |
dc.contributor.author | Wong, WT | en_HK |
dc.date.accessioned | 2010-09-17T10:20:24Z | - |
dc.date.available | 2010-09-17T10:20:24Z | - |
dc.date.issued | 1998 | en_HK |
dc.identifier.citation | Journal of the Chemical Society - Dalton Transactions, 1998 n. 20, p. 3391-3396 | en_HK |
dc.identifier.issn | 0300-9246 | en_HK |
dc.identifier.uri | http://hdl.handle.net/10722/91500 | - |
dc.description.abstract | Five 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.language | eng | en_HK |
dc.relation.ispartof | Journal of the Chemical Society - Dalton Transactions | en_HK |
dc.title | Synthesis and structural characterisation of ruthenium carbonyl clusters containing hydrocarbyl ligands derived from (hydroxy)alkynes HC≡CC(H)(OH)CH3 | en_HK |
dc.type | Article | en_HK |
dc.identifier.email | Wong, WT: wtwong@hku.hk | en_HK |
dc.identifier.authority | Wong, WT=rp00811 | en_HK |
dc.description.nature | link_to_subscribed_fulltext | - |
dc.identifier.doi | 10.1039/A805368E | - |
dc.identifier.scopus | eid_2-s2.0-33748493378 | en_HK |
dc.identifier.hkuros | 40335 | - |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-33748493378&selection=ref&src=s&origin=recordpage | en_HK |
dc.identifier.issue | 20 | en_HK |
dc.identifier.spage | 3391 | en_HK |
dc.identifier.epage | 3396 | en_HK |
dc.identifier.issnl | 0300-9246 | - |