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投稿者: Yuma Morimoto

Article

Tuning the Electronic and Steric Parameters of a Redox-Active Tris(amido) Ligand

Department of Chemistry, University of California, Irvine, California 92697-2025, United States
Inorg. Chem., Article ASAP
DOI: 10.1021/ic401496w
Publication Date (Web): September 6, 2013
Copyright © 2013 American Chemical Society
*E-mail: aheyduk@uci.edu.

Abstract

Abstract Image
A family of tantalum compounds was prepared to probe the electronic effects engendered by the addition of electron-donating or electron-withdrawing groups to the 4/4′ positions of the redox-active ligand derived from bis(2-isopropylamino-4-X-phenyl)amine [X,iPr(NNNcat)H3, X = F, H, Me, tBu]). A general synthetic procedure for the X,iPr(NNNcat)H3 ligand family was developed starting from the 4/4′ disubstituted diphenylamine derivative. A second ligand modification, incorporation of aromatic substituents at the flanking nitrogen moieties, was achieved via palladium-catalyzed cross-coupling to afford bis(2-3,5-dimethylphenylamino-4-methoxy-phenyl)amine OMe,DMP(NNNcat)H3 (DMP = 3,5-C6H3Me2), allowing a comparative study to the less sterically hindered isopropyl derivative. Treatment of the triamines with 1 equiv of TaMe3Cl2 generated the corresponding dichloro complexes X,R(NNNcat)TaCl2(L) (L = empty or Et2O) in high yields. These neutral dichloride derivatives reacted with [NBnEt3][Cl] to produce the anionic trichloride derivatives [NBnEt3][X,R(NNNcat)TaCl3], whereas the neutral dichloride derivatives reacted with chlorine atom donors to produce the neutral trichloride derivatives X,R(NNNsq)TaCl3, containing the one-electron-oxidized form of the redox-active ligand. Aryl azides reacted with the X,R(NNNcat)TaCl2(L) derivatives, resulting in nitrene transfer to tantalum and two-electron oxidation of the ligand platform to giveX,R(NNNq)TaCl2(═NR′) (R = iPr; X = OMe, F, H, Me; R′ = p-C6H4tBu, p-C6H4CF3; and R = 3,5-C6H3Me2; X = OMe; R′ = p-C6H4CH3). Electrochemistry, UV–vis–NIR, IR, and EPR spectroscopies along with X-ray diffraction methods were used to characterize and compare complexes with different redox-active ligand derivatives in each oxidation state. This study demonstrates that while the ligand redox potentials can be adjusted over a 270 mV range through substitutions at the 4/4′ ring positions, the coordination chemistry and reactivity patterns at the bound tantalum center remain unchanged, suggesting that such ligand modifications can be used to tune the redox potentials of a complex for a particular substrate of interest.

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