@article{OberdorfHanftRamleretal.2021,
  author    = {Oberdorf, Kai and Hanft, Anna and Ramler, Jacqueline and Krummenacher, Ivo and Bickelhaupt, Matthias and Poater, Jordi and Lichtenberg, Crispin},
  title     = {Bismuth Amides Mediate Facile and Highly Selective Pn-Pn Radical-Coupling Reactions (Pn=N, P, As)},
  series = {Angewandte Chemie, International Edition},
  volume    = {60},
  journal   = {Angewandte Chemie, International Edition},
  number    = {12},
  doi       = {10.1002/anie.202015514},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-236582},
  pages     = {6441-6445},
  year      = {2021},
  abstract  = {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.},
  language  = {en}
}