Publikationsserver
Bismuth Amides Mediate Facile and Highly Selective Pn–Pn Radical-Coupling Reactions (Pn =N, P, As)
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]C at ambient temperatur...
Сохранить в:
| Главные авторы: | , , , , , , |
|---|---|
| Формат: | Статья |
| Язык: | английский |
| Опубликовано: |
Philipps-Universität Marburg
2023
|
| Предметы: | |
| Online-ссылка: | PDF-полный текст PDF-полный текст |
| Метки: |
Добавить метку
Нет меток, Требуется 1-ая метка записи!
|
| Итог: | 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]C 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 HPnR2 to give R2Pn-PnR2. 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. |
|---|---|
| Объем: | 5 Seiten 42 Seiten |
| DOI: | 10.1002/anie.202015514 |