The electrochemistry of three 1,1'-bis(phosphino)cobaltocenium ligands was examined. Eight new phosphinothioyl and phosphinoselenoyl derivatives were prepared and characterized, and the structures of six of these compounds were determined. The electrochemistry of these phosphinochalcogenyl cobaltocenium compounds displayed reductive waves at potentials less negative than that of the free phosphines. A correlation was found to exist between the Hammett substituent constant and the reduction potentials of these compounds. The electrochemistry of three new and five previously reported transition metal complexes was also examined. Comparison of the electrochemical data with that previously obtained for analogous ferrocenes indicates that a correlation exists between the reduction potentials of the cobaltocenium phosphines and the potentials at which oxidation of the ferrocene phosphines occurs.

Electrochemistry and structural parameter of 1,1'-bis(phosphino)cobaltocenium ligands

243rd National Meeting (2012)

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