Abstract
A family of cationic boron complexes was synthesized, using a dianilidopyridine pincer ligand, which imposes in-plane distortion of the geometry at boron towards T-shaped. Reactivity of these cations toward hydride and base was investigated, and the utility of these cations as precursors to a variety of pi-conjugated BN heterocycles was demonstrated. 300 nm irradiation of a deprotonated pincer boron complex triggered a C-N cleavage/C-C formation yielding a dearomatized boryl imine, which has a structure akin to the long-proposed intermediate in the photochemical Hofmann-Martius rearrangement. The photo-rearrangement triggers relief of the distortion imposed by the pincer ligand.
| Original language | English |
|---|---|
| Pages (from-to) | 4932-4936 |
| Number of pages | 6 |
| Journal | Angewandte Chemie - International Edition |
| Volume | 59 |
| Issue number | 12 |
| DOIs | |
| Publication status | Published - 16 Mar 2020 |
Funding
T.J. thanks the Azrieli Foundation and the Natural Sciences and Engineering Research Council of Canada for postdoctoral fellowships. T.J. thanks Dr. Mark Iron for assistance with computations, Prof. Mordechai Sheves and Dr. Ramprasad Misra for assistance with UV‐vis spectroscopy, and Dr. Michael Rauch and Dr. Vincent Annibale for helpful discussions. D.M. is the Israel Matz Professorial Chair of Organic Chemistry.