Effect of ligand structure, solvent, and temperature ...
|Title||Effect of ligand structure, solvent, and temperature on the electrochemical behavior of polyarene-iron complexes.|
|Author(s)||A. Abd-El-Aziz, C. de Denus, K. Epp, S. Smith, R. Jaeger, D. Pierce|
|Journal||Section Title: Organometallic and Organometalloidal Compounds, Canadian Journal of Chemistry|
|Abstract||The electrochem. study of a no. of polyarene-Fe complexes (e.g., I, 1,4-X,Y; X = Y = O, S) contg. etheric, sulfide, and sulfone bridges indicated that there were various degrees of interaction based on the nature of the bridging heteroatoms. While the electrochem. study of all etheric complexes showed that the metallic moieties behaved as isolated redox centers, there was electronic communication (âˆ¼70-80 mV) for the isomeric sulfide complexes I (1,2-X,Y; X = Y = S) and I (1,4-X,Y; X = Y = S). The rate const. of the following chem. reaction (kf) was calcd. for some of these complexes and these rates were affected by the nature of the solvent, the bridging ligand, and the temp. At various temps., kf indicated a higher degree of stability for complexes contg. sulfide bridges than for those contg. etheric bridges, esp. at room temp. The effect of a strong coordinating solvent, such as MeCN, on the kf of I (1,4-X,Y; X = Y = O) indicated that the substitution of the arene ligand with MeCN mols. proceeded as a dissociative mechanism. Controlled potential coulometry was also used to verify the transfer of two electrons in the 1st redn. process of the di-Fe complexes. [on SciFinder(R)]|
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