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Cationic Bismuth Aminotroponiminates: Charge Controls Redox Properties
Author(s) -
Hanft Anna,
Radacki Krzysztof,
Lichtenberg Crispin
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202005186
Subject(s) - redox , cationic polymerization , bismuth , chemistry , ligand (biochemistry) , cyclic voltammetry , coordination complex , coordination sphere , crystallography , inorganic chemistry , metal , crystal structure , electrochemistry , electrode , polymer chemistry , organic chemistry , biochemistry , receptor
Abstract 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.