Cationic Bismuth Aminotroponiminates: Charge Controls Redox Properties

The behavior of the redox‐active aminotroponiminate (ATI) ligand in the coordination sphere of bismuth has been investigated in neutral and cationic compounds, [Bi(ATI)3] and [Bi(ATI)2Ln][A] (L=neutral ligand; n=0, 1; A=counteranion). Their coordination chemistry in solution and in the solid state has been analyzed through (variable‐temperature) NMR spectroscopy, line‐shape analysis, and single‐crystal X‐ray diffraction analyses, and their Lewis acidity has been evaluated by using the Gutmann–Beckett method (and modifications thereof). Cyclic voltammetry, in combination with DFT calculations, indicates that switching between ligand‐ and metal‐centered redox events is possible by altering the charge of the compounds from 0 in neutral species to +1 in cationic compounds. This adds important facets to the rich redox chemistry of ATIs and to the redox chemistry of bismuth compounds, which is, so far, largely unexplored.
Central control: A series of bismuth aminotroponiminate cations are discussed and differences between neutral and cationic compounds in terms of coordination chemistry, Lewis acidity, and redox behavior are pinpointed. Specifically, cationization allows switching from ligand‐centered redox events to metal‐centered redox events, facilitating rare examples of quasi‐reversible electron transfer at bismuth.