1383804-63-4Relevant academic research and scientific papers
Stepwise intramolecular photoisomerization of NHC-chelate dimesitylboron compounds with C-C bond formation and C-H bond insertion
Rao, Ying-Li,Chen, Leanne D.,Mosey, Nicholas J.,Wang, Suning
, p. 11026 - 11034 (2012/08/28)
C,C-chelate dimesitylboron (BMes2) compounds containing an N-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 A quantitatively, with a high quantum efficiency (0.60-0.75). NMR and single-crystal X-ray diffraction analyses established that the structure of A 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 A 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 A undergo further photoisomerization when irradiated at 350 nm, forming a new colorless species B nearly quantitatively. NMR and single-crystal X-ray diffraction analyses established the structure of isomer 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.
Boron Compounds and Uses Thereof
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Page/Page column 15, (2012/10/08)
Organoboron compounds are described that upon exposure to light absorb light and isomerize and form a dark-colored isomer. The dark-colored isomer converts back to the colorless isomer upon removal of light, or exposure to oxygen or heat. Such compounds c
