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Synthesis and properties of new trinuclear Mo(II) complexes containing imidazole and benzimidazole ferrocene units

Quintal, S., Matos, J., Fonseca, I., Felix, V., Drew, M.G.B., Trindade, N., Meireles, M. and Calhorda, M.J. (2008) Synthesis and properties of new trinuclear Mo(II) complexes containing imidazole and benzimidazole ferrocene units. Inorganica Chimica Acta, 361 (6). pp. 1584-1596. ISSN 0020-1693

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To link to this item DOI: 10.1016/j.ica.2007.05.039

Abstract/Summary

The reaction of FcCOC1 (Fc = (C5H5) Fe(C5H4)) with benzimidazole or imidazole in 1: 1 ratio gives the ferrocenyl derivatives FcCO(benzim) (L1) or FcCO(im) (L2), respectively. Two molecules of L1 or L2 can replace two nitrile ligands in [Mo(eta(3)-C3H5)( CO)(2)(CH3CN)(2)Br] or [Mo(eta(3)-C5H5O)(CO)(2)(CH3CN)(2)Br] leading to the new trinuclear complexes [Mo(eta(3)-C3H5)(CO)(2)(L)(2)Br] (C1 for L = L1; C3 for L = L2) and [Mo(eta(3)-C5H5O)(CO)(2)(L)(2)Br] (C-2 for L = L1; C4 for L = L2) with L1 and L2 acting as N-monodentade ligands. L1, L2 and C2 were characterized by X-ray diffraction studies. [Mo(eta(3)-C5H5O)(CO) 2(L1)(2)Br] was shown to be a trinuclear species, with the two L1 molecules occupying one equatorial and one axial position in the coordination sphere of Mo(II). Cyclic voltammetric studies were performed for the two ligands L1 and L2, as well as for their molybdenum complexes, and kinetic and thermodynamic data for the corresponding redox processes obtained. In agreement with the nature of the frontier orbitals obtained from DFT calculations, L1 and L2 exhibit one oxidation process at the Fe(II) center, while C1, C3, and C4 display another oxidation wave at lower potentials, associated with the oxidation of Mo(II). (C) 2007 Elsevier B. V. All rights reserved.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:11567
Uncontrolled Keywords:ferrocene, molybdenum, trinuclear complexes, cyclic voltammetry, DFT calculations, X-ray structure , DENSITY-FUNCTIONAL THEORY, TUNGSTEN CYCLOPENTADIENONE COMPLEXES, CATALYZED ALLYLIC ALKYLATIONS, AMINO-ACIDS, MOLECULAR-STRUCTURES, ELECTRON-TRANSFER, MOLYBDENUM, PEPTIDES, APPROXIMATION, LIGANDS

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