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Indexed by:期刊论文

Date of Publication:2007-08-01

Journal:EUROPEAN JOURNAL OF INORGANIC CHEMISTRY

Included Journals:SCIE、Scopus

Issue:23

Page Number:3718-3727

ISSN No.:1434-1948

Key Words:biomorganic chemistry; carbonyl displacement; diiron complexes; Fe-only hydrogenase; P ligands

Abstract: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) = PMe(3), L(2) = PMe(2)Ph, 4; PPh(3), 5; PCy(3), 6; P(OEt)(3), 7; L(1)= PMe(2)Ph, L(2) = PPh(3), 8; P(OEt)(3), 9; L(1) = P(OEt)(3), L(2) = PPh(3), 10; PCy(3), 11] and [(mu-edt){Fe(CO)(2)PMe(3))}{Fe(CO)(2)PPh(3)}] (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)PR(3)] subunit were studied using by variable-temperature (31)P{(1)H} 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 PMe(2)Ph ligand in the apical position of the starting complex [(mu-pdt){Fe(CO)(3)}{FeCO(2)(PMe(2)Ph)}] 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)