An unusual trigonal D3 assembly composed of molybdate anions and multiply bonded dimolybdenum units |
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Authors: | Donahue James P Murillo Carlos A |
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Institution: | Department of Chemistry, Tulane University, 6400 Freret Street, New Orleans, LA 70118-5698, United States of America. donahue@tulane.edu |
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Abstract: | Oxidation of the molybdate-linked pair having two quadruply bonded Mo(2)(4+) units, Mo(2)(DAniF)(3)](2)(micro(2)-MoO(4)), (DAniF = N,N'-di-(p-anisyl)formamidinate) leads to the formation of a species consisting of three oxidized Mo(2)(5+) units connected by two micro(3)-MoO(4)(2-) dianions, {Mo(2)(DAniF)(3)](3)(micro(3)-MoO(4))(2)}(2+). This cation displays overall D(3) point group symmetry due to a slight twisting of the three Mo(2)(5+) units about the threefold symmetry axis. This distortion removes all mirror symmetry but preserves all C(2) axes orthogonal to the unique C(3) axis. Cyclic voltammetry of {Mo(2)(DAniF)(3)](3)(micro(3)-MoO(4))(2)}(2+) in CH(2)Cl(2) reveals three reversible one-electron redox processes, corresponding to successive reduction of each of the three Mo(2)(5+) units, with DeltaE(1/2) separations of 0.36 V and 0.41 V. |
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