TY  - JOUR
A1  - Oberdorf, Kai
A1  - Hanft, Anna
A1  - Ramler, Jacqueline
A1  - Krummenacher, Ivo
A1  - Bickelhaupt, Matthias
A1  - Poater, Jordi
A1  - Lichtenberg, Crispin
T1  - Bismuth Amides Mediate Facile and Highly Selective Pn–Pn Radical‐Coupling Reactions (Pn=N, P, As)
JF  - Angewandte Chemie, International Edition
N2  - 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.
KW  - bismuth amides
KW  - radical species
KW  - pnictogen coupling
KW  - aminyl radicals
KW  - diphosphanes
KW  - heavier pnictogens
KW  - radical coupling
Y1  - 2021
U6  - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:bvb:20-opus-236582
VL  - 60
IS  - 12
ER  -