Electrochemical Behavior of Copper Complexes with Substituted Polypyridinic Ligands: An Experimental and Theoretical Study
2008; American Chemical Society; Volume: 47; Issue: 9 Linguagem: Inglês
10.1021/ic702104u
ISSN1520-510X
AutoresWalter Cañón‐Mancisidor, Evgenia Spodine, Diego Venegas‐Yazigi, Darío Rojas, Jorge Manzur, Santiago Álvarez,
Tópico(s)Photochemistry and Electron Transfer Studies
ResumoExperimental redox potentials of the couples [Cu(R−Ln)(CH3CN)]2+,+, where L1 is bis-(pyridine-2-ylmethyl)-benzylamine, L2 is (pyridine-2-ylethyl)(pyridine-2-ylmethyl)-benzylamine, and R is H, Me, or CF3, were determined in dichloromethane solution. The compounds exhibited one simple quasi-reversible wave over the measured potential range of –500 to +1200 mV, and the E1/2 values varied from +200 to +850 mV versus SCE. These experimental values were correlated with redox potentials calculated using density functional theory. The optimized geometries and the predicted redox potentials were obtained using the BP86 functional and a combination of the basis sets LACV3P** (for Cu) and cc-pVTZ(-f) (for light atoms). A distortion analysis of all of the optimized geometries for both oxidation states was performed using the generalized interconversion coordinate φ. A linear relation was obtained between this parameter and the redox potentials. However, the [Cu(CF3−L1)(CH3CN)]+ complex showed the largest deviation, which was explained by the more-rigid structure of the ligand.
Referência(s)