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Article: Polycubane clusters: Synthesis of [Fe4S4(PR3)4]1+,0 (R = Bu(t), Cy, Pr(i)) and [Fe4S4]0 core aggregation upon loss of phosphine

TitlePolycubane clusters: Synthesis of [Fe4S4(PR3)4]1+,0 (R = Bu(t), Cy, Pr(i)) and [Fe4S4]0 core aggregation upon loss of phosphine
Authors
Issue Date1996
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, 1996, v. 118 n. 47, p. 11844-11853 How to Cite?
AbstractThe influence of tertiary phosphines on the stability of FeS3P coordination units and the formation of iron-sulfur clusters has been investigated. Reaction of [Fe4S4Cl4]2- with a small excess of PR3 in acetonitrile/THF affords the cubane-type clusters [Fe4S4(PR3)4]1+ (R = Cy, Bu(t), Pr(i)), one-electron reduced over the initial cluster and possessing an S = 1/4 ground state. These clusters may be electrochemically oxidized to [Fe4S4(PR3)4]2+ and reduced to [Fe4S4(PR3)4], which can also be generated in solution by chemical reduction. The neutral clusters upon standing in solution lose phosphine and aggregate to form dicubane ([Fe8S8(PCy3)6]) or tetracubane ([Fe16S16(PR3)8]; R = Bu(t), Pr(i) clusters. The [Fe8S8]0 dicubane core has two intercubane Fe-S bonds, defining an Fe2S2 rhomb and affording a structure of overall idealized C2(h) symmetry. The tetracubane clusters consist of a cyclic array of four cubanes joined in four Fe2S2 rhombs in a structure of overall D4 symmetry, and present a new structural motif in Fe-S cluster chemistry. Tertiary phosphines impose two significant features on this cluster chemistry. These ligands significantly stabilize the [Fe4S4](1+/0) core oxidation levels compared to the case of conventional [Fe4S4L4]3-,4- clusters (L = monoanion). Ligands with cone angles exceeding that of PEt3 (132°) favor tetrahedral FeS3P coordination sites. This has the effect of directing reactions away from the formation of Fe6S6 (four trigonal pyramidal) and Fe6S8 (six square pyramidal) clusters having the indicated sites which are disfavored by large cone angles. Structural principles governing polycubane clusters together with a brief enumeration of stereochemically feasible polycubanes are presented and discussed.
Persistent Identifierhttp://hdl.handle.net/10722/167547
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorGoh, Cen_US
dc.contributor.authorSegal, BMen_US
dc.contributor.authorHuang, Jen_US
dc.contributor.authorLong, JRen_US
dc.contributor.authorHolm, RHen_US
dc.date.accessioned2012-10-08T03:08:21Z-
dc.date.available2012-10-08T03:08:21Z-
dc.date.issued1996en_US
dc.identifier.citationJournal Of The American Chemical Society, 1996, v. 118 n. 47, p. 11844-11853en_US
dc.identifier.issn0002-7863en_US
dc.identifier.urihttp://hdl.handle.net/10722/167547-
dc.description.abstractThe influence of tertiary phosphines on the stability of FeS3P coordination units and the formation of iron-sulfur clusters has been investigated. Reaction of [Fe4S4Cl4]2- with a small excess of PR3 in acetonitrile/THF affords the cubane-type clusters [Fe4S4(PR3)4]1+ (R = Cy, Bu(t), Pr(i)), one-electron reduced over the initial cluster and possessing an S = 1/4 ground state. These clusters may be electrochemically oxidized to [Fe4S4(PR3)4]2+ and reduced to [Fe4S4(PR3)4], which can also be generated in solution by chemical reduction. The neutral clusters upon standing in solution lose phosphine and aggregate to form dicubane ([Fe8S8(PCy3)6]) or tetracubane ([Fe16S16(PR3)8]; R = Bu(t), Pr(i) clusters. The [Fe8S8]0 dicubane core has two intercubane Fe-S bonds, defining an Fe2S2 rhomb and affording a structure of overall idealized C2(h) symmetry. The tetracubane clusters consist of a cyclic array of four cubanes joined in four Fe2S2 rhombs in a structure of overall D4 symmetry, and present a new structural motif in Fe-S cluster chemistry. Tertiary phosphines impose two significant features on this cluster chemistry. These ligands significantly stabilize the [Fe4S4](1+/0) core oxidation levels compared to the case of conventional [Fe4S4L4]3-,4- clusters (L = monoanion). Ligands with cone angles exceeding that of PEt3 (132°) favor tetrahedral FeS3P coordination sites. This has the effect of directing reactions away from the formation of Fe6S6 (four trigonal pyramidal) and Fe6S8 (six square pyramidal) clusters having the indicated sites which are disfavored by large cone angles. Structural principles governing polycubane clusters together with a brief enumeration of stereochemically feasible polycubanes are presented and discussed.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.titlePolycubane clusters: Synthesis of [Fe4S4(PR3)4]1+,0 (R = Bu(t), Cy, Pr(i)) and [Fe4S4]0 core aggregation upon loss of phosphineen_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/ja9620200en_US
dc.identifier.scopuseid_2-s2.0-0029853710en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0029853710&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume118en_US
dc.identifier.issue47en_US
dc.identifier.spage11844en_US
dc.identifier.epage11853en_US
dc.identifier.isiWOS:A1996VV33700018-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridGoh, C=36785572400en_US
dc.identifier.scopusauthoridSegal, BM=7102467604en_US
dc.identifier.scopusauthoridHuang, J=7407192639en_US
dc.identifier.scopusauthoridLong, JR=7403447252en_US
dc.identifier.scopusauthoridHolm, RH=7202326371en_US

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