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The First Designed Syntheses of Bis-dimetal Molecules in Which the Bridges Are Diamidate Ligands

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posted on 28.02.2002, 00:00 by F. Albert Cotton, Lee M. Daniels, James P. Donahue, Chun Y. Liu, Carlos A. Murillo
The first deliberate syntheses of molecules in which pairs of quadruply bonded Mo2 units are bridged by N,N‘-diarylterephthaloyldiamidate (aryl = Ph, m-CF3Ph) ligands are described. The addition of neutral N,N‘-diarylterephthaloyldiamide to 2 equiv of [Mo2(DAniF)3(MeCN)2]+ (DAniF = N,N‘-di-p-anisylformamidinate) followed by the introduction of excess H3CO- in MeCN results in the formation of (DAniF)3Mo2{(C6H5)NC(O)C6H4(O)CN(C6H5)}Mo2(DAniF)3 (1) and (DAniF)3Mo2{[(m-CF3)C6H5]NC(O)C6H4(O)CN[(m-CF3)C6H5]}Mo2(DAniF)3 (2). The ΔE1/2 for the oxidation of each Mo2 unit is greater for these terephthaloyldiamidate-bridged molecules (∼100 mV) than for the analogous terephthalate-bridged compound (∼60 mV). Variation in the nature of the substituents on the diamidate nitrogen atoms offers a means to fine-tune the oxidation potentials of the Mo2 units.