Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 27, Issue 20, Pages 6230-6239Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.202005186
Keywords
aminotroponiminates; bismuth; cationic species; redox chemistry; redox-active ligands
Categories
Funding
- Fonds der Chemischen Industrie
- Deutsche Forschungsgemeinschaft
- Projekt DEAL
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The study investigates the behavior of the redox-active aminotroponiminate (ATI) ligand in neutral and cationic bismuth compounds. The results show that switching between ligand- and metal-centered redox events is possible by altering the charge of the compounds. This adds important facets to the rich redox chemistry of ATIs and bismuth compounds.
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)(2)L-n][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.
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