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Article: Mercury-osmium carbonyl clusters resulting from facile Hg-C bond cleavage: reactions of [Os3H2(CO)10] with [Hg(C≡CPh)2] and [RHgC≡CHgR] (R = Ph, Me or Et)

TitleMercury-osmium carbonyl clusters resulting from facile Hg-C bond cleavage: reactions of [Os3H2(CO)10] with [Hg(C≡CPh)2] and [RHgC≡CHgR] (R = Ph, Me or Et)
Authors
Issue Date1996
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, 1996, p. 899-911 How to Cite?
AbstractReaction of the unsaturated cluster [Os3H2(CO)10] with Hg(C[triple bond, length half m-dash]CPh)2 afforded two new Os–Hg clusters cis-[Os(CO)4{(µ-Hg)Os3(CO)10(µ-η2-CH[double bond, length half m-dash]CHPh)}2]1 and [{Os3(CO)10(µ-η2-CH[double bond, length half m-dash]CHPh)}2(µ4-Hg)]2 in 30 and 20% yield, respectively. Cluster 1 consists of two (µ-Hg)Os3(CO)10(µ-η2-CH[double bond, length half m-dash]CHPh) subunits bonded to a central Os(CO)4 moiety in the cis configuration which under ambient conditions converts into 2 over 3–5 d with the extrusion of a HgOs(CO)4 unit. Cluster 2 comprises two skewed Os–Hg metal butterflies sharing a common wingtip Hg atom. In refluxing tetrahydrofuran (66 °C)2 underwent redistribution with the symmetrical mercurials [Hg{M(CO)3(η5-C5H5)}2](M = Cr, Mo or W) to afford respectively the heterometallic clusters [{Os3(CO)10(µ-η2-CH[double bond, length half m-dash]CHPh)}(µ3-Hg){M(CO)3(η5-C5H5)}](M = Cr 3, Mo 4 or W 5) in moderate yield. Alternatively, 3–5 can be obtained more readily from the reaction of cluster 1 with the corresponding symmetric mercurials at room temperature. Reactions of [Os3H2(CO)10] with [RHgC[triple bond, length half m-dash]CHgR](R = Ph, Me or Et) afforded the clusters [{Os3(CO)10(µ-η2-CH[double bond, length half m-dash]CH2)}(µ4-Hg){Os3(CO)10(µ-H)}]6(12%) and [{Os3(CO)10(µ-η2-CH[double bond, length half m-dash]CH2)}2(µ4-Hg)]7(25%). Cluster 7 is isostructural with 2, whilst 6 bears a central Hg atom connecting two structurally different osmium triangles. Clusters 1, 2, 6 and 7 all result from Hg–C bond cleavage of the parent organomercury species, hence the generality of this cleavage is demonstrated. The new clusters 1, 2, 4, 6 and 7 have been fully characterised by both spectroscopic and crystallographic techniques.
Persistent Identifierhttp://hdl.handle.net/10722/69652
ISSN
2002 Impact Factor: 3.023
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DC FieldValueLanguage
dc.contributor.authorAu, YKen_HK
dc.contributor.authorWong, WTen_HK
dc.date.accessioned2010-09-06T06:15:37Z-
dc.date.available2010-09-06T06:15:37Z-
dc.date.issued1996en_HK
dc.identifier.citationJournal of the Chemical Society Dalton Transactions, 1996, p. 899-911en_HK
dc.identifier.issn1472-7773en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69652-
dc.description.abstractReaction of the unsaturated cluster [Os3H2(CO)10] with Hg(C[triple bond, length half m-dash]CPh)2 afforded two new Os–Hg clusters cis-[Os(CO)4{(µ-Hg)Os3(CO)10(µ-η2-CH[double bond, length half m-dash]CHPh)}2]1 and [{Os3(CO)10(µ-η2-CH[double bond, length half m-dash]CHPh)}2(µ4-Hg)]2 in 30 and 20% yield, respectively. Cluster 1 consists of two (µ-Hg)Os3(CO)10(µ-η2-CH[double bond, length half m-dash]CHPh) subunits bonded to a central Os(CO)4 moiety in the cis configuration which under ambient conditions converts into 2 over 3–5 d with the extrusion of a HgOs(CO)4 unit. Cluster 2 comprises two skewed Os–Hg metal butterflies sharing a common wingtip Hg atom. In refluxing tetrahydrofuran (66 °C)2 underwent redistribution with the symmetrical mercurials [Hg{M(CO)3(η5-C5H5)}2](M = Cr, Mo or W) to afford respectively the heterometallic clusters [{Os3(CO)10(µ-η2-CH[double bond, length half m-dash]CHPh)}(µ3-Hg){M(CO)3(η5-C5H5)}](M = Cr 3, Mo 4 or W 5) in moderate yield. Alternatively, 3–5 can be obtained more readily from the reaction of cluster 1 with the corresponding symmetric mercurials at room temperature. Reactions of [Os3H2(CO)10] with [RHgC[triple bond, length half m-dash]CHgR](R = Ph, Me or Et) afforded the clusters [{Os3(CO)10(µ-η2-CH[double bond, length half m-dash]CH2)}(µ4-Hg){Os3(CO)10(µ-H)}]6(12%) and [{Os3(CO)10(µ-η2-CH[double bond, length half m-dash]CH2)}2(µ4-Hg)]7(25%). Cluster 7 is isostructural with 2, whilst 6 bears a central Hg atom connecting two structurally different osmium triangles. Clusters 1, 2, 6 and 7 all result from Hg–C bond cleavage of the parent organomercury species, hence the generality of this cleavage is demonstrated. The new clusters 1, 2, 4, 6 and 7 have been fully characterised by both spectroscopic and crystallographic techniques.-
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.titleMercury-osmium carbonyl clusters resulting from facile Hg-C bond cleavage: reactions of [Os3H2(CO)10] with [Hg(C≡CPh)2] and [RHgC≡CHgR] (R = Ph, Me or Et)en_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=1472-7773&volume=&spage=899&epage=911&date=1996&atitle=Mercury-osmium+carbonyl+clusters+resulting+from+facile+Hg-C+bond+cleavage:++reactions+of+[Os3H2(CO)10]+with+[Hg(CbaCPh)2]+and+[RHgCbaCHgR]+(R+=+Ph,+Me+or+Et)en_HK
dc.identifier.emailWong, WT: wtwong@hku.hken_HK
dc.identifier.authorityWong, WT=rp00811en_HK
dc.identifier.doi10.1039/DT9960000899-
dc.identifier.hkuros21861en_HK
dc.identifier.hkuros14627-
dc.identifier.spage899-
dc.identifier.epage911-
dc.identifier.isiWOS:A1996UC26200015-
dc.publisher.placeUnited Kingdom-

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