Controlled Redox Chemistry at Cerium within a Tripodal Nitroxide Ligand Framework |
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| Authors: | Justin A Bogart Connor A Lippincott Dr Patrick J Carroll Dr Corwin H Booth Prof Eric J Schelter |
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| Institution: | 1. P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 S. 34th St., Philadelphia, PA 19104 (USA);2. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (USA) |
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| Abstract: | Ligand reorganization has been shown to have a profound effect on the outcome of cerium redox chemistry. Through the use of a tethered, tripodal, trianionic nitroxide ligand, ((2‐tBuNOH)C6H4CH2)3N]3? (TriNOx3?), controlled redox chemistry at cerium was accomplished, and typically reactive complexes of tetravalent cerium were isolated. These included rare cationic complexes Ce(TriNOx)thf]BArF4], in which ArF=3,5‐(CF3)2‐C6H3, and Ce(TriNOx)py]OTf]. A rare complete Ce–halide series, Ce(TriNOx)X, in which X=F?, Cl?, Br?, I?, was also synthesized. The solution chemistry of these complexes was explored through detailed solution‐phase electrochemistry and 1H NMR experiments and showed a unique shift in the ratio of species with inner‐ and outer‐sphere anions with size of the anionic X? group. DFT calculations on the series of calculations corroborated the experimental findings. |
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| Keywords: | cerium density functional calculations electrochemistry nitroxides redox chemistry |
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