Electrochemical Behavior of Copper Complexes with Substituted Polypyridinic Ligands: An Experimental and Theoretical Study

详细信息    查看全文

• 作者：Walter Ca&#xf1 ; on-Mancisidor ; Evgenia Spodine ; Diego Venegas-Yazigi ; Darí ; o Rojas ; Jorge Manzur ; Santiago Alvarez
• 刊名：Inorganic Chemistry
• 出版年：2008
• 出版时间：May 5, 2008
• 年：2008
• 卷：47
• 期：9
• 页码：3687 - 3692
• 全文大小：295K
• 年卷期：v.47,no.9(May 5, 2008)
• ISSN：1520-510X

文摘

Experimental 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 E_1/2 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.