Kai Oberdorf1, Anna Hanft2, Jacqueline Ramler3, Ivo Krummenacher2, Matthias Bickelhaupt4, Jordi Poater5, Crispin Lichtenberg6. 1. University of Wurzburg: Julius-Maximilians-Universitat Wurzburg, Inorganic Chemistry, GERMANY. 2. Julius Maximilians University Würzburg: Julius-Maximilians-Universitat Wurzburg, Inorganic Chemistry, GERMANY. 3. Julius-Maximilians-Universität Würzburg: Julius-Maximilians-Universitat Wurzburg, Inorganic Chemistry, GERMANY. 4. Vrije Universiteit Amsterdam, Theoretical Chemistry, NETHERLANDS. 5. Universitat de Barcelona, Theoretical Chemistry, SPAIN. 6. Julius-Maximilians-Universität Würzburg, Institut für Anorganische Chemie, Am Hubland, 97074, Würzburg, GERMANY.
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 homologs 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.
The controlled release of well-defined radical spn>ecies under mild conditions for subsequent use in selective reactions is an impn>ortant and challenging tn>an class="Chemical">ask 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 homologs 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.
Authors: Julia Haak; Julia Krüger; Nikolay V Abrosimov; Christoph Helling; Stephan Schulz; George E Cutsail Iii Journal: Inorg Chem Date: 2022-07-14 Impact factor: 5.436
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