TY - JOUR
T1 - A Crystalline Bismuth(II) Radical Anion: Synthesis, Characterization, and Reactivity
AU - Pavlidis, Sotirios
AU - Teutloff, Christian
AU - Buzanich, Ana Guilherme
AU - Krause, Konstantin B.
AU - Emmerling, Franziska
AU - Bittl, Robert
AU - Abbenseth, Josh
PY - 2025/10/12
Y1 - 2025/10/12
N2 - We 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 behavior, as shown by single-electron transfer chemistry and radical coupling reactions.
AB - We 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 behavior, as shown by single-electron transfer chemistry and radical coupling reactions.
KW - Bismuth
KW - EPR spectroscopy
KW - EXAFS
KW - Radicals
KW - XANES
UR - https://www.scopus.com/pages/publications/105018697096
U2 - 10.1002/anie.202515545
DO - 10.1002/anie.202515545
M3 - Article
SN - 1521-3773
JO - Angewandte Chemie International Edition
JF - Angewandte Chemie International Edition
M1 - e202515545
ER -