Nitrosyl Derivatives of Diiron(I) Dithiolates Mimic the Structure and Lewis Acidity of the [FeFe]-Hydrogenase Active Site.
This study probes the impact of electronic asymmetry of diiron(l) dithiolato carbonyls. Treatment of Fe(SCH)(CO)(PMe) compounds (n = 2, 3; x = 1, 2, 3) with NOBF gave the derivatives [Fe(SCH)(CO)(PMe)(NO)]BF, which are electronically unsymmetrical because of the presence of a single NO ligand. Where...
| Publicado en: | Journal of the American Chemical Society Vol. 130; no. 36; pp. 12021 - 12031 |
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| Autores principales: | , , , , |
| Formato: | Artículo |
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American Chemical Society
9/10/2008
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| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=34350851&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 34350851 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 9/10/2008 vid: 130 iid: 36 pid: 997 pub: American Chemical Society artinfo: ui: 34350851 10.1021/ja802268p ppf: 12021 ppct: 10 formats: tig: atl: Nitrosyl Derivatives of Diiron(I) Dithiolates Mimic the Structure and Lewis Acidity of the [FeFe]-Hydrogenase Active Site. aug: au: Olsen, Matthew T. Bruschi, Maurizio De Gioia, Luca Rauchfuss, Thomas B. Wilson, Scott A. affil: Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801 Department of Biotechnology and Biosciences, University of Milano—Bicocca, Piazza della Scienza 1, 20126 Milan, Italy su: Organoiron compounds Density functionals Enantiomers Electrons Electrophiles sug: subj: Organoiron compounds Density functionals Enantiomers Electrons Electrophiles ab: This study probes the impact of electronic asymmetry of diiron(l) dithiolato carbonyls. Treatment of Fe(SCH)(CO)(PMe) compounds (n = 2, 3; x = 1, 2, 3) with NOBF gave the derivatives [Fe(SCH)(CO)(PMe)(NO)]BF, which are electronically unsymmetrical because of the presence of a single NO ligand. Whereas the monophosphine derivative is largely undistorted, the bis(PMe) derivatives are distorted such that the CO ligand on the Fe(CO)(PMe)(NO) subunit is semibridging. Two isomers of [Fe(SCH)(CO)(PMe)(NO)]BF were characterized spectroscopically and crystallographically. Each isomer features electron-rich Fe(CO)PMe and electrophilic Fe(CO)(PMe)(NO) subunits. These species are in equilibrium with an unobserved isomer that reversibly binds CO (ΔH = -35 kJ/mol, ΔS = -139 J mol K) to give the symmetrical adduct [Fe(SCH)(μ-NO)(CO)(PMe)]BF. In contrast to Fe(SCH)(CO)(PMe), the bis(PMe) nitrosyl complexes readily undergo CO substitution to give the (PMe) derivatives. The nitrosyl complexes reduce at potentials that are ~1 V milder than their carbonyl counterparts. Results of density functional theory calculations, specifically natural bond orbital analysis, reinforce the electronic resemblance of the nitrosyl complexes to the corresponding mixed-valence diiron complexes. Unlike other diiron dithiolato carbonyls, these species undergo reversible reductions at mild potentials. The results show that the novel structural and chemical features associated with mixed-valence diiron dithiolates (the so-called H models) can be replicated in the absence of mixed-valency by the introduction of electronic asymmetry. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2008 holdings: @attributes: islocal: N |
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