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Phosphane and phosphite unsymmetrically disubstituted diiron complexes related to the Fe-only hydrogenase active site
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2007 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-0682, no 23, 3718-3727 p.Article in journal (Refereed) Published
Abstract [en]

A series of unsymmetrically disubstituted diiron complexes [(mu-pdt){Fe(CO)(2)L-1]{Fe(CO)(2)L-2}] [pdt = 1,3-propanedithiolato; L-1 = PMe3, L-2 = PMe2Ph, 4; PPh3, 5; PCy3, 6; P(OEt)(3), 7; L-1= PMe2Ph, L-2 = PPh3, 8; P(OEt)(3), 9; L-1 = P(OEt)(3), L-2 = PPh3, 10; PCy3, 11] and [(mu-edt){Fe(CO)(2)PMe3)}{Fe(CO)(2)PPh3}] (edt = 1, 2-ethane dithiolato, 12) were prepared by means of step-wise CO displacements of [(mu-pdt)Fe-2(CO)(6)] and [(mu-edt)-Fe-2(CO)(6)] by different tertiary phosphane and phosphite ligands. The interconversion of the irondithiacyclohexane ring and the rotation of the [Fe(CO)(2)PR3] subunit were studied using by variable-temperature P-31{H-1} NMR spectroscopy of 4, 6 and 12 in solution. The molecular structures of 4-6, 8-10 and 12 show that complexes 4-6, 8, 9 and 12 possess an apical/basal coordination mode and complex 10 has an apical/apical conformation. The X-ray analyses indicate that the PMe2Ph ligand in the apical position of the starting complex [(mu-pdt){Fe(CO)(3)}{FeCO2(PMe2Ph)}] rotates to the basal position on conversion to the products 8 and 9. Cyclic voltammograms of 4-11 were studied both under argon and CO. The influences of the phosphane and phosphite ligands on the redox properties of the unsymmetrically disubstituted diiron complexes are discussed. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Place, publisher, year, edition, pages
2007. no 23, 3718-3727 p.
Keyword [en]
biomorganic chemistry, carbonyl displacement, diiron complexes, Fe-only hydrogenase, P ligands, iron hydrogenase, model complexes, electrochemical properties, coordination, exchange, ligands, evolution, analogs
URN: urn:nbn:se:kth:diva-16893DOI: 10.1002/ejic.200601184ISI: 000248936200014ScopusID: 2-s2.0-34548074196OAI: diva2:334936
QC 20100525Available from: 2010-08-05 Created: 2010-08-05Bibliographically approved

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Sun, Licheng
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