摘要：

We have prepared and structurally characterized six-coordinate Fe(II), Co(II), and Ni(II) complexes of types [M II(HL 1) 2(H 2O) 2][ClO 4] 2 (M = Fe, 1; Co, 3; and Ni, 5) and [M II(HL 2) 3][ClO 4] 2 · MeCN (M = Fe, 2 and Co, 4) of bidentate pyridine amide ligands, N-(phenyl)-2-pyridinecarboxamide (HL 1) and N-(4-methylphenyl)-2-pyridinecarboxamide (HL 2). 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 HL 1 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 HL 2 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 [M II(HL 1) 2(H 2O) 2][ClO 4] 2 (M = Cu and Zn) and [Co III(L 2) 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.

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