Stepwise Intramolecular Photoisomerization of NHC-Chelate Dimesitylboron Compounds with C–C Bond Formation and C–H Bond Insertion

Abstract

C,C-chelate dimesitylboron (BMes₂) compounds containing an <i>N</i>-heterocyclic carbene (NHC) donor have been obtained. Single-crystal X-ray diffraction analyses established that the boron atom in these compounds is bound by four carbon atoms in a distorted tetrahedral geometry. Compared to previously reported N,C-chelate dimesitylboron compounds, the new C,C-chelate boron compounds have a much larger HOMO–LUMO energy gap (>3.60 eV). They do, however, respond to UV irradiation (300 nm) in the same manner as N,C-chelate BMes₂ compounds do, undergoing photoisomerization and converting to an intensely colored (yellow or orange) isomer <b>A</b> quantitatively, with a high quantum efficiency (0.60–0.75). NMR and single-crystal X-ray diffraction analyses established that the structure of <b>A</b> is similar to the dark isomers obtained from N,C-chelate BMes₂ compounds. However, unlike the N,C-chelate dark isomers that have the tendency to thermally reverse back to the light colored isomers, the isomers <b>A</b> of the C,C-chelate BMes₂ are thermally stable and no reverse isomerization was observed even when heated to 80 °C (or 110 °C) for hours. The most unusual finding is that isomers <b>A</b> undergo further photoisomerization when irradiated at 350 nm, forming a new colorless species <b>B</b> nearly quantitatively. NMR and single-crystal X-ray diffraction analyses established the structure of isomer <b>B</b>, which may be considered as an intramolecular C–H insertion product via a borylene intermediate. Mechanistic aspects of this unusual two-step photoisomerization process have been examined by DFT computational studies