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Article: Synthesis and structural characterisation of ruthenium and osmium carbonyl clusters containing organomercurials

TitleSynthesis and structural characterisation of ruthenium and osmium carbonyl clusters containing organomercurials
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. 15, p. 2497-2510 How to Cite?
AbstractReaction of the activated cluster [Os3(CO)10(NCMe)2] with [PhHgS(C5H4N)] afforded two new Os-Hg clusters cis-[Os(CO)4{Os3(CO)10(μ-η 2-SC5H4N)(μ-Hg)}2] 1 and [{Os3(CO)10(μ-η2-SC5H 4N)}2(μ4-Hg)] 2 in 25 and 30% yields, respectively. Cluster 1 consists of two {Os3(CO)10(μ-η2-SC5H 4N)(μ-Hg)} subunits bonded to a central Os(CO)4 moiety in a cis configuration. Cluster 2 comprises two skewed Os-Hg metal butterflies sharing a common wingtip Hg atom. Treatment of the same organomercurial with [Ru3(CO)10(NCMe)2] produced the cluster compound cis-[Ru(CO)4{Ru3(CO)9(μ-η 3-SC5H4N)(μ-Hg)}2] 3 (48%). This has a metal skeleton similar to that of 2 with the {S(C5H4N)} ligand moiety bonding to the ruthenium atoms in a μ-η3 fashion. Treatment of [Os3(CO)10(NCMe)2] with [PhHg(mbt)] (Hmbt = 2-mercaptobenzothiazole) afforded [{Os3(CO)10(μ-η2-mbt)} 2(μ4-Hg)] 4 (35%) and [Os3(CO)10(μ-η2-mbt)(μ-η 2-Hg(mbt)] 5 (20%). Cluster 4 is very similar to 2, but the S(C5H4N) ligand is replaced by the mbt ligand, while 5 consists of an Os3 triangle having one edge spanned by both [μ-η2-mbt] and [μ-η2-Hg(mbt)] moieties. The reaction of [Os5C(CO)15] and [Ru3(CO)12] with another class of organomercurial (diphenylthiocarbazono)phenylmercury reagent [PhHgL′] [L′ = SC(N=NPh)(=NNHPh)] containing a N=N functionality under thermal conditions produced [{Os5C(CO)14(μ-η2-SPh)} 2(μ4-Hg)] 6 (26%) and [{Os5C(CO)14(μ-η2-L′)} 2(μ4-Hg)] 7 (34%) and [Ru2(CO)4Ph{μ-η2-C(O)Ph}(μ 2-S)(μ-η2-L′)] 8 (15%), [Ru2(CO)4(C(O)Ph) {μ-η2-C(O)Ph}(μ2-S)(μ-η 2-L′)] 9 (15%) and [{Ru(CO)2Ph}2(μ-η2-L′)] 10 (45%), respectively. In clusters 6 and 7, two {Os5C(CO)14} subunits linked by a common wingtip mercury atom, are bonded with both μ-η2-SPh in 6 and μ-η2-L′ in 7. However, in the case of complexes 8, 9 and 10, only binuclear ruthenium carbonyl complexes formed instead of the expected formation of mixed-metal clusters. Complexes 1-10 result from the cleavage of both Hg-C and Hg-S bonds in the parent organomercury species. All these complexes have been fully characterized by both spectroscopic and crystallographic techniques.
Persistent Identifierhttp://hdl.handle.net/10722/70518
ISSN
1999 Impact Factor: 2.31
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorKong, FSen_HK
dc.contributor.authorWong, WTen_HK
dc.date.accessioned2010-09-06T06:23:37Z-
dc.date.available2010-09-06T06:23:37Z-
dc.date.issued1999en_HK
dc.identifier.citationJournal Of The Chemical Society - Dalton Transactions, 1999 n. 15, p. 2497-2510en_HK
dc.identifier.issn0300-9246en_HK
dc.identifier.urihttp://hdl.handle.net/10722/70518-
dc.description.abstractReaction of the activated cluster [Os3(CO)10(NCMe)2] with [PhHgS(C5H4N)] afforded two new Os-Hg clusters cis-[Os(CO)4{Os3(CO)10(μ-η 2-SC5H4N)(μ-Hg)}2] 1 and [{Os3(CO)10(μ-η2-SC5H 4N)}2(μ4-Hg)] 2 in 25 and 30% yields, respectively. Cluster 1 consists of two {Os3(CO)10(μ-η2-SC5H 4N)(μ-Hg)} subunits bonded to a central Os(CO)4 moiety in a cis configuration. Cluster 2 comprises two skewed Os-Hg metal butterflies sharing a common wingtip Hg atom. Treatment of the same organomercurial with [Ru3(CO)10(NCMe)2] produced the cluster compound cis-[Ru(CO)4{Ru3(CO)9(μ-η 3-SC5H4N)(μ-Hg)}2] 3 (48%). This has a metal skeleton similar to that of 2 with the {S(C5H4N)} ligand moiety bonding to the ruthenium atoms in a μ-η3 fashion. Treatment of [Os3(CO)10(NCMe)2] with [PhHg(mbt)] (Hmbt = 2-mercaptobenzothiazole) afforded [{Os3(CO)10(μ-η2-mbt)} 2(μ4-Hg)] 4 (35%) and [Os3(CO)10(μ-η2-mbt)(μ-η 2-Hg(mbt)] 5 (20%). Cluster 4 is very similar to 2, but the S(C5H4N) ligand is replaced by the mbt ligand, while 5 consists of an Os3 triangle having one edge spanned by both [μ-η2-mbt] and [μ-η2-Hg(mbt)] moieties. The reaction of [Os5C(CO)15] and [Ru3(CO)12] with another class of organomercurial (diphenylthiocarbazono)phenylmercury reagent [PhHgL′] [L′ = SC(N=NPh)(=NNHPh)] containing a N=N functionality under thermal conditions produced [{Os5C(CO)14(μ-η2-SPh)} 2(μ4-Hg)] 6 (26%) and [{Os5C(CO)14(μ-η2-L′)} 2(μ4-Hg)] 7 (34%) and [Ru2(CO)4Ph{μ-η2-C(O)Ph}(μ 2-S)(μ-η2-L′)] 8 (15%), [Ru2(CO)4(C(O)Ph) {μ-η2-C(O)Ph}(μ2-S)(μ-η 2-L′)] 9 (15%) and [{Ru(CO)2Ph}2(μ-η2-L′)] 10 (45%), respectively. In clusters 6 and 7, two {Os5C(CO)14} subunits linked by a common wingtip mercury atom, are bonded with both μ-η2-SPh in 6 and μ-η2-L′ in 7. However, in the case of complexes 8, 9 and 10, only binuclear ruthenium carbonyl complexes formed instead of the expected formation of mixed-metal clusters. Complexes 1-10 result from the cleavage of both Hg-C and Hg-S bonds in the parent organomercury species. All these complexes have been fully characterized by both spectroscopic and crystallographic techniques.en_HK
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 and structural characterisation of ruthenium and osmium carbonyl clusters containing organomercurialsen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1472-7773&volume=15&spage=2497&epage=2510&date=1999&atitle=Synthesis+and+structural+characterisation+of+ruthenium+and+osmium+carbonyl+clusters+containing+organomercurialsen_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1039/A902701G-
dc.identifier.scopuseid_2-s2.0-33748610816en_HK
dc.identifier.hkuros49864en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-33748610816&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.issue15en_HK
dc.identifier.spage2497en_HK
dc.identifier.epage2510en_HK
dc.identifier.isiWOS:000081767900015-
dc.identifier.scopusauthoridKong, FS=7201837458en_HK
dc.identifier.scopusauthoridWong, WT=7403973084en_HK

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