Synthesis, structure, and properties of monomeric Fe(II), Co(II), and Ni(II) complexes of neutral N-(aryl)-2-pyridinecarboxamides

Jacob, Wilson ; Mukherjee, Rabindra Nath (2006) Synthesis, structure, and properties of monomeric Fe(II), Co(II), and Ni(II) complexes of neutral N-(aryl)-2-pyridinecarboxamides Inorganica Chimica Acta, 359 (14). pp. 4565-4573. ISSN 0020-1693

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Official URL: http://linkinghub.elsevier.com/retrieve/pii/S00201...

Related URL: http://dx.doi.org/10.1016/j.ica.2006.07.003

Abstract

We have prepared and structurally characterized six-coordinate Fe(II), Co(II), and Ni(II) complexes of types [MII(HL1)2(H2O)2][ClO4]2 (M = Fe, 1; Co, 3; and Ni, 5) and [MII(HL2)3][ClO4]2·MeCN (M = Fe, 2 and Co, 4) of bidentate pyridine amide ligands, N-(phenyl)-2-pyridinecarboxamide (HL1) and N-(4-methylphenyl)-2-pyridinecarboxamide (HL2). The metal centers in bis(ligand)-diaqua complexes 1, 3 and 5 are coordinated by two pyridyl N and two amide O atoms from two HL1 ligands and six-coordination is completed by coordination of two water molecules. The complexes are isomorphous and possess trans-octahedral geometry. The metal centers in isomorphous tris(ligand) complexes 2 and 4 are coordinated by three pyridyl N and three amide O atoms from three HL2 ligands. The relative dispositions of the pyridine N and amide O atoms reveal that the pseudo-octahedral geometry have the meridional stereochemistry. To the best of our knowledge, this work provides the first examples of structurally characterized six-coordinate iron(II) complexes in which the coordination is solely by neutral pyridine amide ligands providing pyridine N and amide O donor atoms, with or without water coordination. Careful analyses of structural parameters of 1-5 along with that reported in the literature [MII(HL1)2(H2O)2][ClO4]2 (M = Cu and Zn) and [CoIII(L2)3] have allowed us to arrive at a number of structural correlations/generalizations. The complexes are uniformly high-spin. Spectroscopic (IR and UV/Vis) and redox properties of the complexes have also been investigated.

Item Type:Article
Source:Copyright of this article belongs to Elsevier Science.
Keywords:Fe(II); Co(II) and Ni(II) Complexes; Bidentate Pyridine Amide Ligands; Crystal Structures; Pyridine N and Amide O Coordination; Absorption Spectra and Magnetism (high-spin Complexes)
ID Code:26008
Deposited On:04 Dec 2010 10:40
Last Modified:02 Mar 2011 11:19

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