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- Title
Synthesis and Reactivity of Cationic Boron Complexes Distorted by Pyridine‐based Pincer Ligands: Isolation of a Photochemical Hofmann–Martius‐type Intermediate.
- Authors
Janes, Trevor; Diskin‐Posner, Yael; Milstein, David
- 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 π‐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.
- Subjects
BORON; HYDRIDES; HETEROCYCLIC compounds; CATIONS; IRRADIATION
- Publication
Angewandte Chemie, 2020, Vol 132, Issue 12, p4962
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202000406