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• W2007444172 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 Mössbauer, and paramagnetic 1H NMR spectroscopy. These complexes are found to be localized on the 57Fe Mössbauer 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) Å, b = 20.610(3) Å, c = 13.326(3) Å, β = 92.74(2)°, Z = 4, Dcalcd = 2.029 g cm-3, RF = 0.033, RwF = 0.036. The neutral compound 1‘,2‘,1‘‘‘-triethylbiferrocene crystallizes in the triclinic space group P1̄ with two molecules in a unit cell with dimensions a = 7.465(3), b = 8.419(2), c = 18.581(4) Å and α = 87.83(2), β = 87.98(3), γ = 64.27(2)°; RF = 0.021 and RwF = 0.029." @default.
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• W2007444172 date "1996-01-01" @default.
• W2007444172 modified "2023-10-17" @default.
• W2007444172 title "Effects of Zero-Point Energy Difference on Intramolecular Electron Transfer in Asymmetric Polyethyl-Substituted Biferrocenium Triiodides" @default.
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• W2007444172 doi "https://doi.org/10.1021/ic950953b" @default.
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