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Asymmetric heterobimetallic mixed-valence complex trans-[(SO3)Co(cyclam)(NCS)Ru(NH3)4(NCS)](BF4): Synthesis and characterization |
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| Authors: | Maria Aparecida S. SilvaTé rcio de F. Paulo,Solange de O. PinheiroAlzir A. Batista,Javier EllenaEduardo H.S. Sousa,Luiz G. de F. LopesIzaura C.N. Dió genes |
| Affiliation: | a Departmento de Química Orgânica e Inorgânica, Universidade Federal do Ceará, Cx. Postal 6021, Campus do Pici, Fortaleza, Ceará, Brazil b Departamento de Química, Universidade Federal de São Carlos, Cx. Postal 676, 13565-905 São Carlos, SP, Brazil c Instituto de Física de São Carlos, USP, Cx. Postal 780, 13560-250 São Carlos, SP, Brazil |
| Abstract: | [(SO3)Co(cyclam)(NCS)] and [(SO3)Co(cyclam)-NCS-Ru(NH3)4(NCS)](BF4) complexes were synthesized and characterized by means of X-ray diffraction, electrochemistry, elemental analysis, and spectroscopic techniques. Crystallographic and FTIR data indicated NCS− ligand is coordinated to Co through the nitrogen atom in the monomer species. Electrochemistry and FTIR data of the material isolated after reductive electrolysis of [(SO3)Co(cyclam)(NCS)] hint that NCS− and SO32− are released thus forming [Co(cyclam)(L)2]2+, where L is solvent molecules. The formation of the heterobimetallic mixed-valence complex induced a thermodynamic stabilization of Co and Ru metal atoms in the oxidized and reduced states, respectively. According to the Robin and Day classification, a Class II system with a comproportionation constant of 5.78 × 106 is suggested for the mixed-valence complex based on the electrochemical and UV-Vis-NIR results. |
| Keywords: | Coordination chemistry Mixed valence Macrocyclic ligand Bridging ligand Thiocyanate Intervalence charge transfer |
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