期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 60, 期 12, 页码 6441-6445出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202015514
关键词
aminyl radicals; bismuth amides; diphosphanes; heavier pnictogens; radical coupling
The controlled release of aminyl radicals from bismuth amide species at ambient temperature enables selective N-N coupling reactions to yield hydrazines. Analyzes using various spectroscopy techniques and calculations reveal low homolytic bond-dissociation energies, suggesting radical coupling in the coordination sphere of bismuth, and demonstrate the effectiveness of electronic and steric parameters in controlling these reactions.
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(NAr2)(3)] readily release aminyl radicals [NAr2](.) at ambient temperature in solution. These reactions yield the corresponding hydrazines, Ar2N-NAr2, 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.
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