TY  - JOUR
A1  - Pavlidis, Sotirios
A1  - Teutloff, Christian
A1  - de Oliveira Guilherme Buzanich, Ana
A1  - Krause, Konstantin B.
A1  - Emmerling, Franziska
A1  - Bittl, Robert
A1  - Abbenseth, Josh
T1  - A Crystalline Bismuth(II) Radical Anion: Synthesis, Characterization, and Reactivity
JF  - Angewandte Chemie International Edition
N2  - AbstractWe report the synthesis of a planarized tris‐amidobismuthane supported by a rigid, bulky NNN pincer ligand, which enforces a T‐shaped geometry at the bismuth center. The Bi(NNN) complex features a low‐lying LUMO with distinct Bi(6p) orbital character as shown by DFT calculations. Cyclic voltammetry reveals a fully reversible one‐electron reduction at E1/2 = –1.85 V versus Fc0/+ in THF. Chemical reduction with KC8 in the presence of 4,7,13,16,21,24‐hexaoxa‐1,10‐diazabicyclo[8.8.8]hexacosane (222‐crypt) enables the isolation of an unprecedented Bi(II) radical anion in high isolated yields. Multi‐frequency EPR, X‐ray absorption spectroscopy and SQUID magnetometry complemented by theoretical calculations confirm localization of the unpaired electron on the bismuth center. Preliminary reactivity studies display radical reactivity as shown by single‐electron transfer chemistry and radical coupling reactions.
KW  - Bi(III)
PY  - 2025
UR  - https://nbn-resolving.org/urn:nbn:de:kobv:b43-644143
DO  - https://doi.org/10.1002/anie.202515545
SN  - 1433-7851
VL  - 64
IS  - 49
SP  - 1
EP  - 6
PB  - Wiley VHC-Verlag
AN  - OPUS4-64414
LA  - eng
AD  - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER  -