Abstract
In this report, two new binuclear mixed-valence (MV) compounds and their one-electron oxidation products, [MeCpLRu(μ-CN)Fe(dppe)Cp][PF6]n (L = dppe, (PPh3)2) (n = 1, 2), were synthesized and thoroughly characterized by single-crystal X-ray diffraction analysis. Complexes 12+ and 22+ are one-electron oxidation products of 11+ and 2+, respectively. The electronic absorption results indicate that there exists metal to metal charge transfer (MMCT) in the one-electron oxidation products, which is strongly supported by the theoretical calculations. Complexes 12+ and 22+ can be defined as Class II MV compounds. It is found that the MMCT band is obviously red-shifted on going from 12+ to 22+, because the donating electron ability of (PPh3)2 is stronger than that of dppe.
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