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Synthesis, spectroscopic characterization and electrochemical behaviour of nickel(II) complexes with C-meso-5,5,7,12,12,14-hexamethylcyclotetradecane (Me6[14]aneN4). Crystal structure of {Ni(Me6[14]aneN4)|I2

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A series of complexes of formula {Ni(Me6[14]aneN4)X2| (Me6[14]aneN4) = C-meso-5,5,7,12,12,14-hexamethyl-1,4,-8,11-tetraazacyclotetradecane and X = N3 (1), NCO (2), NCS (3), AcO (4) or I (5) has been synthesized. The crystal structure of (5) has been determined by X-ray diffraction methods. The nickel atom is surrounded by a square-planar array of nitrogen atoms, giving a low-spin complex. The macrocyclic ligand shows the most stable conformation, the six-membered rings exhibiting the chair form while the gauche conformation is adopted by the five-membered rings. Spectroscopic and magnetic data for (1)–(4) are consistent with octahedral coordination around the nickel atom, which is achieved by four N atoms of the macrocyclic ligand in a single plane and by two azido-N (1), cyanato-N (2), thiocyanato-N (3) and carboxylato-O (4) groups occupying the axial positions. An electrochemical study of the oxidation of (1)–(5) has been carried out in nonaqueous solvents and the prospects of synthesis of the corresponding nickel(III) species are discussed in the light of the electrochemical data.

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Authors and Affiliations

  1. Departament de Química Inorgànica, Facultat de Química de la Universitat de Valéncia, Dr. Moliner 50, 46100, Burjassot(València), Spain

    Rafael Ruiz & Miguel Julve

  2. Departamento de Química, Universidad Politécnica de Valéncia, Camino de Vera s/n, 46071, Valéncia, Spain

    Carmen Muñoz & Jorgel Payá

  3. Departamento de Fisica Aplicada, Universidad Politécnica de Valéncia, Camino de Vera s/n, 46071, Valéncia, Spain

    Juan Cano, Juan Soto, Ramón Martínez-Máñez & Carmen Muñoz

  4. Departamento de Ingemiería de la Constructión, Universidad Politécnica de Valéncia, Camino de Vera s/n, 46071, Valéncia, Spain

    Jorgel Payá

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  1. Rafael Ruiz
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  2. Miguel Julve
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Ruiz, R., Julve, M., Cano, J. et al. Synthesis, spectroscopic characterization and electrochemical behaviour of nickel(II) complexes with C-meso-5,5,7,12,12,14-hexamethylcyclotetradecane (Me6[14]aneN4). Crystal structure of {Ni(Me6[14]aneN4)|I2 . Transition Met Chem 18, 523–527 (1993). https://doi.org/10.1007/BF00136619

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  • DOI: https://doi.org/10.1007/BF00136619

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