Synthesis and Reactivity of Cationic Boron Complexes Distorted by Pyridine-based Pincer Ligands: Isolation of a Photochemical Hofmann–Martius-type Intermediate

Trevor Janes, Yael Diskin-Posner, David Milstein

Research output: Contribution to journalArticle

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.

Original languageEnglish
Pages (from-to)4932-4936
Number of pages5
JournalAngewandte Chemie - International Edition
Volume59
Issue number12
DOIs
Publication statusPublished - Mar 16 2020

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Keywords

  • BN heterocycles
  • C−C bond formation
  • Hofmann–Martius rearrangement
  • boron cations
  • pincer ligands

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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