Abstract
The syntheses, characterizations, and physical properties of asymmetric polyethyl-substituted mixed-valence 1‘,2‘,1‘‘‘-triethylbiferrocenium triiodide (15), 1‘,3‘,1‘‘‘-triethylbiferrocenium triiodide (16), and 1‘,2‘,1‘‘‘,3‘‘‘-tetraethylbiferrocenium triiodide (17) are described. Complexes 15−17 were characterized by electrochemical measurements and by near-IR, 57Fe Mossbauer, and paramagnetic 1H NMR spectroscopy. These complexes are found to be localized on the 57Fe Mossbauer time scale (electron-transfer rates less than 107 s-1). The cations in complexes 15−17 are not in equivalent environments. This asymmetry results in a nonzero zero-point energy barrier for intramolecular electron transfer. Analysis of the sign of contact shifts suggests that the electron delocalization in 15−17 is based on competing σ and π delocalization mechanisms. The X-ray structure of 15 has been determined at 298 K: monoclinic, P21/n, a = 9.962(3) A, b = 20.610(3) A, c = 13.326(3) A, β = 92.74(2)°, Z = 4, Dcalcd = 2.029 g cm-3...
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