A Crystalline Bismuth(II) Radical Anion: Synthesis, Characterization, and Reactivity
Abstract
Abstract 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 E 1/2 = –1.85 V versus Fc 0/+ in THF. Chemical reduction with KC 8 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.
Article Details
Authors (7)
Sotirios Pavlidis
Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany
Christian Teutloff
Ana Guilherme Buzanich
Department of Materials Chemistry, Federal Institute for Materials Research and Testing, Richard-Willstätter-Str. 11, 12489 Berlin, Germany
Konstantin B. Krause
Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489 Berlin, Germany
Franziska Emmerling
Department of Materials Chemistry, Federal Institute for Materials Research and Testing, Richard-Willstätter-Str. 11, 12489 Berlin, Germany
Robert Bittl
Fachbereich Physik Freie Universität Berlin 14195 Berlin Germany
Josh Abbenseth
Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489 Berlin, Germany