File Download

There are no files associated with this item.

  Links for fulltext
     (May Require Subscription)
Supplementary

Article: On the Existence in Solution of Doubly Thiolate-Bridged Double Cubanes Containing the Heterometal [MFe3S4] Core (M = Mo, W)

TitleOn the Existence in Solution of Doubly Thiolate-Bridged Double Cubanes Containing the Heterometal [MFe3S4] Core (M = Mo, W)
Authors
Issue Date1997
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 1997, v. 36 n. 3, p. 356-361 How to Cite?
AbstractClusters of the general type {[MFe3S4(SR)2(cat)]2(μ 2-SR)2}4- (cat = catecholate) have previously been shown to contain two heterometal cubane-type cores [MFe3S4]3+ (M = Mo, W) linked by two Fe-S(R)-M bridges such that the cluster has idealized centrosymmetry. These clusters resemble the P-clusters of nitrogenase in that both have two μ2-SR bridges between cubane (or cuboidal) halves of the cluster. When dissolved in a strongly coordinating solvent or treated with a suitable ligand L1-,0, the bridges are cleaved to afford the single cubanes [MFe3S4(SR)3(cat)L/(solv)]2-,3-. Because of their relation to P-clusters, the stability and electron transfer properties of the double cubanes have been examined in solution. 1H NMR spectroscopic and cyclic voltammetric properties of acetonitrile solutions prepared from Et4N+ salts of clusters with R = Et and M = Mo, W are entirely consistent with the presence of bridged double cubanes in solution. Key observations include different chemical shifts of bridging and terminal ethanethiolate ligands and two successive oxidations separated by 150-230 mV. Reduction occurs with twice the diffusion current of the oxidations and results in cleavage to two single cubanes. Bridge strength increases in the order R = Ph < Et (consistent with basicities of the thiolate anions) and M = Mo < W. This work has produced the first demonstration that doubly thiolate-bridged double cubanes of any description remain intact in solution. The synthesis of Fe4S4 double cubanes with bis(μ2-SR) bridges persists as an objective if actual analogues of the P-cluster are to be obtained.
Persistent Identifierhttp://hdl.handle.net/10722/167416
ISSN
2015 Impact Factor: 4.82
2015 SCImago Journal Rankings: 1.873
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorHuang, Jen_US
dc.contributor.authorGoh, Cen_US
dc.contributor.authorHolm, RHen_US
dc.date.accessioned2012-10-08T03:06:43Z-
dc.date.available2012-10-08T03:06:43Z-
dc.date.issued1997en_US
dc.identifier.citationInorganic Chemistry, 1997, v. 36 n. 3, p. 356-361en_US
dc.identifier.issn0020-1669en_US
dc.identifier.urihttp://hdl.handle.net/10722/167416-
dc.description.abstractClusters of the general type {[MFe3S4(SR)2(cat)]2(μ 2-SR)2}4- (cat = catecholate) have previously been shown to contain two heterometal cubane-type cores [MFe3S4]3+ (M = Mo, W) linked by two Fe-S(R)-M bridges such that the cluster has idealized centrosymmetry. These clusters resemble the P-clusters of nitrogenase in that both have two μ2-SR bridges between cubane (or cuboidal) halves of the cluster. When dissolved in a strongly coordinating solvent or treated with a suitable ligand L1-,0, the bridges are cleaved to afford the single cubanes [MFe3S4(SR)3(cat)L/(solv)]2-,3-. Because of their relation to P-clusters, the stability and electron transfer properties of the double cubanes have been examined in solution. 1H NMR spectroscopic and cyclic voltammetric properties of acetonitrile solutions prepared from Et4N+ salts of clusters with R = Et and M = Mo, W are entirely consistent with the presence of bridged double cubanes in solution. Key observations include different chemical shifts of bridging and terminal ethanethiolate ligands and two successive oxidations separated by 150-230 mV. Reduction occurs with twice the diffusion current of the oxidations and results in cleavage to two single cubanes. Bridge strength increases in the order R = Ph < Et (consistent with basicities of the thiolate anions) and M = Mo < W. This work has produced the first demonstration that doubly thiolate-bridged double cubanes of any description remain intact in solution. The synthesis of Fe4S4 double cubanes with bis(μ2-SR) bridges persists as an objective if actual analogues of the P-cluster are to be obtained.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/icen_US
dc.relation.ispartofInorganic Chemistryen_US
dc.titleOn the Existence in Solution of Doubly Thiolate-Bridged Double Cubanes Containing the Heterometal [MFe3S4] Core (M = Mo, W)en_US
dc.typeArticleen_US
dc.identifier.emailHuang, J:jshuang@hkucc.hku.hken_US
dc.identifier.authorityHuang, J=rp00709en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ic960844c-
dc.identifier.scopuseid_2-s2.0-0013674698en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0013674698&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume36en_US
dc.identifier.issue3en_US
dc.identifier.spage356en_US
dc.identifier.epage361en_US
dc.identifier.isiWOS:A1997WF34700018-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridHuang, J=7407192639en_US
dc.identifier.scopusauthoridGoh, C=36785572400en_US
dc.identifier.scopusauthoridHolm, RH=7202326371en_US

Export via OAI-PMH Interface in XML Formats


OR


Export to Other Non-XML Formats