Journal
INORGANICA CHIMICA ACTA
Volume 359, Issue 7, Pages 1997-2003Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2006.01.013
Keywords
manganese(III) complexes; phenolate schiff bases; N2O2 donors; electronic spectra; X-ray structure; electrochemistry
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A series of mononuclear manganese(III) complexes of formulae (Mn(L)(X)(H2O)] (1-13) and [Mn(L)(X)] (14-17) (X = ClO4, F, Cl, Br, I, NCS, N-3), derived from the Schiff bases of 5-bromosalicylaldehyde and different types of diamine (1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane and 1,4-diaminobutane), have been synthesized and characterized by the combination of IR, UV-Vis spectroscopies, cyclic voltammetry and by X-ray crystallography. The redox properties of all the manganese(III) complexes show grossly identical features consisting of a reversible or quasireversible Mn-III/Mn-II reduction. Besides Mn-III/Mn-II reduction, the complexes 4, 5, 10, 13 and 16 also show reversible or quasi reversible Mn-III/Mn-IV oxidation. A linear correlation has been found for the complexes 5, 7, 11 and 13 [Mn(L-2)(X)(H2O)] (X = F, Cl, Br, I) when E-1/2 [Mn-III/Mn-II] is plotted against Mulliken electronegativities (chi(M)). The effect of the flexibility of the ligand on redox potential has been studied. It has been observed that the manganese(II) state is stabilized with increasing flexibility of the ligand environment. The crystal structure of 6 shows an octahedral geometry. (c) 2006 Elsevier B.V. All rights reserved.
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