Herein, we report the synthesis, isolation and characterization of two cationic organobismuth(II) compounds bearing N,C,N pincer frameworks, which are crucial intermediates in bismuth radical processes. X-ray crystallography uncovered a monomeric Bi(II) structure, while SQUID magnetometry in combination with NMR and EPR spectroscopy provide evidence for a para-magnetic S = 1/2 state. High resolution multifrequency EPR at X, Q, and W-band enable the precise assignment of the full g- and 209Bi A-tensors. Experimental data and DFT calculations reveal both complexes are metal-centered radicals with little delocalization onto the ligands.
Synthesis, Isolation and Characterization of Two Cationic Organo-bismuth(II) Pincer Complexes Relevant in Radical Redox Chemistry