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Article: Synthesis, Identification, and Reactivity Properties of Symmetrical MoFe3S4 Double Cubanes with Fe-S-Fe and Fe-O-Fe Bridges

TitleSynthesis, Identification, and Reactivity Properties of Symmetrical MoFe3S4 Double Cubanes with Fe-S-Fe and Fe-O-Fe Bridges
Authors
Issue Date1998
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/ic
Citation
Inorganic Chemistry, 1998, v. 37 n. 9, p. 2247-2254 How to Cite?
AbstractSingly bridged double cubane clusters containing Fe4S4 and/or MoFe3S4 cores and linked by an Fe-S-Fe unit bear an interesting compositional similarity to the cofactor of nitrogenase and constitute a nearly unexplored class of clusters. We have expanded recently our investigation of the prototypic cluster {[(Meida)MoFe3S4Cl2]2-(μ 2-S)}4- (6) (Huang et al.; J. Am. Chem. Soc. 1997, 119, 8662) to other types {[(Meida)MoFe3S4L2l2(μ 2-S)}4- (L = EtS-, ArO- (8-10)) (Meida = N-methylimidodiacetate(2-)). Clusters are formed by coupling reactions of the single cubanes [(Meida)MoFe3S4L3]2- (L = Cl- (1), ArO- (3-5) at their substitutionally labile iron sites with primarily Li2S. Using 2 NaOEt/H2O as an oxide source in Me2SO, the oxo-bridged clusters {[(Meida)-MoFe3S4L2l2(μ 2-O)}4- (L = Cl- (13), ArO- (14, 15)) have been prepared. All double cubanes were obtained as a mixture of as many as four diastereomers. Double cubane structures were established by NMR and electrochemical criteria. Both the sulfido- and oxo-bridged clusters undergo terminal ligand substitution reactions with bridge retention. Oxo bridges are much more susceptible than sulfido bridges to protic cleavage with water, (Et3NH)Cl, ArOH, and HS-. Reaction of 13 with hydrosulfide affords a second route to 6. These and other results define a set of reactions that are regiospecific at either the terminal ligand or bridge sites and provide a basis for future reactivity manipulation of symmetrical and unsymmetrical bridged double cubanes.
Persistent Identifierhttp://hdl.handle.net/10722/167324
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.authorHolm, RHen_US
dc.date.accessioned2012-10-08T03:05:40Z-
dc.date.available2012-10-08T03:05:40Z-
dc.date.issued1998en_US
dc.identifier.citationInorganic Chemistry, 1998, v. 37 n. 9, p. 2247-2254en_US
dc.identifier.issn0020-1669en_US
dc.identifier.urihttp://hdl.handle.net/10722/167324-
dc.description.abstractSingly bridged double cubane clusters containing Fe4S4 and/or MoFe3S4 cores and linked by an Fe-S-Fe unit bear an interesting compositional similarity to the cofactor of nitrogenase and constitute a nearly unexplored class of clusters. We have expanded recently our investigation of the prototypic cluster {[(Meida)MoFe3S4Cl2]2-(μ 2-S)}4- (6) (Huang et al.; J. Am. Chem. Soc. 1997, 119, 8662) to other types {[(Meida)MoFe3S4L2l2(μ 2-S)}4- (L = EtS-, ArO- (8-10)) (Meida = N-methylimidodiacetate(2-)). Clusters are formed by coupling reactions of the single cubanes [(Meida)MoFe3S4L3]2- (L = Cl- (1), ArO- (3-5) at their substitutionally labile iron sites with primarily Li2S. Using 2 NaOEt/H2O as an oxide source in Me2SO, the oxo-bridged clusters {[(Meida)-MoFe3S4L2l2(μ 2-O)}4- (L = Cl- (13), ArO- (14, 15)) have been prepared. All double cubanes were obtained as a mixture of as many as four diastereomers. Double cubane structures were established by NMR and electrochemical criteria. Both the sulfido- and oxo-bridged clusters undergo terminal ligand substitution reactions with bridge retention. Oxo bridges are much more susceptible than sulfido bridges to protic cleavage with water, (Et3NH)Cl, ArOH, and HS-. Reaction of 13 with hydrosulfide affords a second route to 6. These and other results define a set of reactions that are regiospecific at either the terminal ligand or bridge sites and provide a basis for future reactivity manipulation of symmetrical and unsymmetrical bridged double cubanes.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.titleSynthesis, Identification, and Reactivity Properties of Symmetrical MoFe3S4 Double Cubanes with Fe-S-Fe and Fe-O-Fe Bridgesen_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/ic971353a-
dc.identifier.scopuseid_2-s2.0-0001140422en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0001140422&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume37en_US
dc.identifier.issue9en_US
dc.identifier.spage2247en_US
dc.identifier.epage2254en_US
dc.identifier.isiWOS:000073506700024-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridHuang, J=7407192639en_US
dc.identifier.scopusauthoridHolm, RH=7202326371en_US

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