Three‐coordinate cationic bismuth compounds [Bi(diaryl)(EPMe\(_{3}\))][SbF\(_{6}\)] have been isolated and fully characterized (diaryl=[(C\(_{6}\)H\(_{4}\))\(_{2}\)C\(_{2}\)H\(_{1}\)]\(^{2-}\), E=S, Se). They represent rare examples of molecular complexes with Bi⋅⋅⋅EPR\(_{3}\) interactions (R=monoanionic substituent). The \(^{31}\)P NMR chemical shift of EPMe3 has been found to be sensitive to the formation of LA⋅⋅⋅EPMe\(_{3}\) Lewis acid/base interactions (LA=Lewis acid). This corresponds to a modification of the Gutmann–Beckett method and reveals information about the hardness/softness of the Lewis acid under investigation. A series of organobismuth compounds, bismuth halides, and cationic bismuth species have been investigated with this approach and compared to traditional group 13 and cationic group 14 Lewis acids. Especially cationic bismuth species have been shown to be potent soft Lewis acids that may prefer Lewis pair formation with a soft (S/Se‐based) rather than a hard (O/N‐based) donor. Analytical techniques applied in this work include (heteronuclear) NMR spectroscopy, single‐crystal X‐ray diffraction analysis, and DFT calculations.

The controlled release of well‐defined radical species under mild conditions for subsequent use in selective reactions is an important and challenging task in synthetic chemistry. We show here that simple bismuth amide species [Bi(NAr\(_2\))\(_3\)] readily release aminyl radicals [NAr\(_2\)]. at ambient temperature in solution. These reactions yield the corresponding hydrazines, Ar\(_2\)N−NAr\(_2\), as a result of highly selective N−N coupling. The exploitation of facile homolytic Bi−Pn bond cleavage for Pn−Pn bond formation was extended to higher homologues of the pnictogens (Pn=N–As): homoleptic bismuth amides mediate the highly selective dehydrocoupling of HPnR\(_2\) to give R\(_2\)Pn−PnR\(_2\). Analyses by NMR and EPR spectroscopy, single‐crystal X‐ray diffraction, and DFT calculations reveal low Bi−N homolytic bond‐dissociation energies, suggest radical coupling in the coordination sphere of bismuth, and reveal electronic and steric parameters as effective tools to control these reactions.

Major advances in the chemistry of 5th and 6th row heavy p-block element compounds have recently uncovered intriguing reactivity patterns towards small molecules such as H\(_2\), CO\(_2\), and ethylene. However, well-defined, homogeneous insertion reactions with carbon monoxide, one of the benchmark substrates in this field, have not been reported to date. We demonstrate here, that a cationic bismuth amide undergoes facile insertion of CO into the Bi–N bond under mild conditions. This approach grants direct access to the first cationic bismuth carbamoyl species. Its characterization by NMR, IR, and UV/vis spectroscopy, elemental analysis, single-crystal X-ray analysis, cyclic voltammetry, and DFT calculations revealed intriguing properties, such as a reversible electron transfer at the bismuth center and an absorption feature at 353 nm ascribed to a transition involving σ- and π-type orbitals of the bismuth-carbamoyl functionality. A combined experimental and theoretical approach provided insight into the mechanism of CO insertion. The substrate scope could be extended to isonitriles.