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Article: Molybdenum - Iron sulfide-bridged double cubanes

TitleMolybdenum - Iron sulfide-bridged double cubanes
Authors
Issue Date1997
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html
Citation
Journal Of The American Chemical Society, 1997, v. 119 n. 37, p. 8662-8674 How to Cite?
AbstractA new class of clusters, sulfide-bridged double cubanes containing the units MFE3(μ3-S)4 M = Fe, Mo), has been investigated a possible synthetic precursors to the iron-molybdenum cofactor (FeMoco) of nitrogenase. Clusters containing the symmetric core structures [Fe4Q4-Q-Fe4Q4]2+ (11-13), Q = S, Se) have been prepared by the coupling of separate cubane clusters [Fe4S4Cl4]2+, [Fe4Q4(LS3)Cl]2+, where LS3 = 1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p -tolylthio)benzenate(3-)). Similarly, the cuboidal cluster [VFe4S6(PEt3)4Cl] was coupled to form [VFe4S6(PEt3)4]2S (14). The cluster [(Fe4S4Cl3)2S]4- (11) is the first structurally proven example of the class (Challen, P. R.; Koo, S.-M.; Dunham, W. R.; Coucouvanis, D.J. Am. Chem. Soc. 1990, 112, 2455). Bridged structures have also been established crystallographically for {[Fe4Se4(LS3)]2Se}4- (13) and 14. Other criteria for identification of this structure developed using 11-14 are coupled redox processes in cyclic voltammetry and the detection of intact double cubane ions by electrospray mass spectrometry. For the coupling of heterometal cubanes, the Mo site was protected by chelation with Meida (N-methylimidodiacetate(2-)) as in [(Meida)MoFe3Sc4Cl3]2- (6), thereby directing the bridging reaction to the Fe sites. The structures of two [VFe3S4]2+ cubane clusters containing the tricoordinate (Meida) V fragment are reported. The reaction system 6/Li2S afforded {[(Meida)MoFe3S4Cl2]2S}4- (15). The symmetrical sulfide-bridged double cubane structure of 15 has been established by the electrochemical and mass spectrometric criteria and by the existence of the four isomers consistent with this structure. The equimolar reaction system 6[Fe4S4Cl4]2-/Li2S produced a mixture of {[(Meida)MoFe3S4Cl2]S(Fe4S4Cl3}4- (17), 15, and 11. Cluster 17 is also formed in the system 15/[Fe4S4Cl4]2-. The unsymmetrical sulfide-bridged double cubane structure of 17 was established by mass spectrometry and detection of the two isomers consistent with this structure. In the first reaction system, the product mole ratio 17:15 ~ 3:1 is explained in terms of differential steric hindrance of conformation arising from rotation around the Fe-S-Fe bridge. The cored composition of double cubane 15 (Mo2-Fe6S9) approaches that of FeMoco (MoFe7S9). The core composition of 17 is exactly the same as FeMoco; 17 is the first synthetic cluster with this property.
Persistent Identifierhttp://hdl.handle.net/10722/167565
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorHuang, Jen_US
dc.contributor.authorMukerjee, Sen_US
dc.contributor.authorSegal, BMen_US
dc.contributor.authorAkashi, Hen_US
dc.contributor.authorZhou, Jen_US
dc.contributor.authorHolm, RHen_US
dc.date.accessioned2012-10-08T03:08:34Z-
dc.date.available2012-10-08T03:08:34Z-
dc.date.issued1997en_US
dc.identifier.citationJournal Of The American Chemical Society, 1997, v. 119 n. 37, p. 8662-8674en_US
dc.identifier.issn0002-7863en_US
dc.identifier.urihttp://hdl.handle.net/10722/167565-
dc.description.abstractA new class of clusters, sulfide-bridged double cubanes containing the units MFE3(μ3-S)4 M = Fe, Mo), has been investigated a possible synthetic precursors to the iron-molybdenum cofactor (FeMoco) of nitrogenase. Clusters containing the symmetric core structures [Fe4Q4-Q-Fe4Q4]2+ (11-13), Q = S, Se) have been prepared by the coupling of separate cubane clusters [Fe4S4Cl4]2+, [Fe4Q4(LS3)Cl]2+, where LS3 = 1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p -tolylthio)benzenate(3-)). Similarly, the cuboidal cluster [VFe4S6(PEt3)4Cl] was coupled to form [VFe4S6(PEt3)4]2S (14). The cluster [(Fe4S4Cl3)2S]4- (11) is the first structurally proven example of the class (Challen, P. R.; Koo, S.-M.; Dunham, W. R.; Coucouvanis, D.J. Am. Chem. Soc. 1990, 112, 2455). Bridged structures have also been established crystallographically for {[Fe4Se4(LS3)]2Se}4- (13) and 14. Other criteria for identification of this structure developed using 11-14 are coupled redox processes in cyclic voltammetry and the detection of intact double cubane ions by electrospray mass spectrometry. For the coupling of heterometal cubanes, the Mo site was protected by chelation with Meida (N-methylimidodiacetate(2-)) as in [(Meida)MoFe3Sc4Cl3]2- (6), thereby directing the bridging reaction to the Fe sites. The structures of two [VFe3S4]2+ cubane clusters containing the tricoordinate (Meida) V fragment are reported. The reaction system 6/Li2S afforded {[(Meida)MoFe3S4Cl2]2S}4- (15). The symmetrical sulfide-bridged double cubane structure of 15 has been established by the electrochemical and mass spectrometric criteria and by the existence of the four isomers consistent with this structure. The equimolar reaction system 6[Fe4S4Cl4]2-/Li2S produced a mixture of {[(Meida)MoFe3S4Cl2]S(Fe4S4Cl3}4- (17), 15, and 11. Cluster 17 is also formed in the system 15/[Fe4S4Cl4]2-. The unsymmetrical sulfide-bridged double cubane structure of 17 was established by mass spectrometry and detection of the two isomers consistent with this structure. In the first reaction system, the product mole ratio 17:15 ~ 3:1 is explained in terms of differential steric hindrance of conformation arising from rotation around the Fe-S-Fe bridge. The cored composition of double cubane 15 (Mo2-Fe6S9) approaches that of FeMoco (MoFe7S9). The core composition of 17 is exactly the same as FeMoco; 17 is the first synthetic cluster with this property.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.htmlen_US
dc.relation.ispartofJournal of the American Chemical Societyen_US
dc.titleMolybdenum - Iron sulfide-bridged double cubanesen_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/ja971401qen_US
dc.identifier.scopuseid_2-s2.0-0030930687en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0030930687&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume119en_US
dc.identifier.issue37en_US
dc.identifier.spage8662en_US
dc.identifier.epage8674en_US
dc.identifier.isiWOS:A1997XW69600010-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridHuang, J=7407192639en_US
dc.identifier.scopusauthoridMukerjee, S=7103054643en_US
dc.identifier.scopusauthoridSegal, BM=7102467604en_US
dc.identifier.scopusauthoridAkashi, H=7103188287en_US
dc.identifier.scopusauthoridZhou, J=7405552141en_US
dc.identifier.scopusauthoridHolm, RH=7202326371en_US

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