Coordination Chemistry of Amine Bis(phenolate) Cobalt(II), Nickel(II), and Copper(II) Complexes
| Autor: | María L. Durán, Antonio Sousa-Pedrares, Antonio Sousa, José A. García-Vázquez, Elena Labisbal, Laura Rodríguez, José Real, Jaime Romero |
|---|---|
| Rok vydání: | 2006 |
| Předmět: |
chemistry.chemical_classification
Ligand Metal ions in aqueous solution Inorganic chemistry chemistry.chemical_element Crystal structure Copper Coordination complex Inorganic Chemistry chemistry.chemical_compound Nickel chemistry Polymer chemistry Physical and Theoretical Chemistry Acetonitrile Cobalt |
| Zdroj: | Inorganic Chemistry. 45:7903-7914 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/ic0602594 |
| Popis: | Cobalt(II), nickel(II), and copper(II) (1, 2, and 3) complexes of the dianionic form of the bis(phenolate) ligand N,N-bis(3,4-dimethyl-2-hydroxybenzyl)-N',N'-dimethylethylenediamine (H2L) have been synthesized by electrochemical oxidation of the appropriate metal in an acetonitrile solution of the ligand. When copper is used as the anode, the addition of 1,10-phenanthroline to the electrolytic phase gave rise to a different compound [CuL]2.2CH3CN (4). The compounds [CoL]2.2CH3CN (1), [Ni2L2(H2O)].H2O (2), [CuL]2.3H2O (3), and [CuL]2.2CH3CN (4) were characterized by microanalysis, IR, electronic spectroscopy, FAB mass spectrometry, magnetic measurements and by single-crystal X-ray diffraction. The crystal structures show that the complexes have a dinuclear structure. In compounds 1, 3, and 4, two metal ions are coordinated by the two amine nitrogens and the two phenol oxygen atoms of a deprotonated pendant phenol ligand, with one phenolic oxygen atom from ligand acting as a bridge. In compounds 1 and 3, each metal center has a geometry that is closest to trigonal bipyramidal. Magnetic susceptibility data for both compounds show an antiferromagnetic coupling with 2J = -15 cm(-1) for the cobalt(II) complex and a strong antiferromagnetic coupling with 2J = -654 cm(-1) for the copper(II) complex. However, in 4 the geometry around the metal is closer to square pyramidal and the compound shows a lower antiferromagnetic coupling (2J = -90 cm(-1)) than in 3. The nickel atoms in the dimeric compound 2 are hexacoordinate. The NiN2O4 chromophore has a highly distorted octahedral geometry. In this structure, a dianionic ligand binds to one nickel through the two amine nitrogen atoms and the two oxygen atoms and to an adjacent nickel via one of these oxygen atoms. The nickel atoms are linked through a triple oxygen bridge involving two phenolic oxygens, each from a different ligand, and an oxygen atom from a water molecule. The two nickel ions in 2 are ferromagnetically coupled with 2J = 19.8 cm(-1). |
| Databáze: | OpenAIRE |
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