Abstract
Abstract1,3‐Dimethylimidazol‐2‐ylidene difluoroborane (NHC‐BF2H) was prepared in a one‐pot, two‐step reaction from the parent ligated borane (NHC‐BH3). The derived difluoroboryl radical (NHC‐BF2.) was generated by laser flash photolysis experiments and characterized by UV spectroscopy and rate‐constant measurements. It is transient and reacts quickly with O2. Unusually, it also reacts more rapidly with ethyl vinyl ether than with methyl acrylate. By this measure, it is the first electrophilic ligated boryl radical. Both NHC‐BH3 and NHC‐BF2H serve as co‐initiators in bulk photopolymerizations, converting both electron‐poor and electron‐rich monomers at roughly similar rates. However, the difluorinated coinitiator provides polymers with dramatically increased chain lengths from both monomers.
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