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Bismuth Amides Mediate Facile and Highly Selective Pn–Pn Radical‐Coupling Reactions (Pn=N, P, As)
Author(s) -
Oberdorf Kai,
Hanft Anna,
Ramler Jacqueline,
Krummenacher Ivo,
Bickelhaupt F. Matthias,
Poater Jordi,
Lichtenberg Crispin
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202015514
Subject(s) - homolysis , chemistry , radical , bismuth , bond cleavage , homoleptic , steric effects , electron paramagnetic resonance , amide , photochemistry , coupling reaction , dissociation (chemistry) , coordination sphere , crystallography , crystal structure , stereochemistry , organic chemistry , catalysis , nuclear magnetic resonance , metal , physics
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.