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The first pyrroloazaphosphinines with nitrogen at the junction, 7a and 7b, have been prepared by a special route involving the collapse of the phosphorus bridges of appropriate 7‐phosphanorbornenes. The parent molecule 7a has a strictly planar azaphosphinine ring with some electronic delocalization according to DFT computations. Its P=C double bond does not react with 2,3‐dimethylbutadiene unless...
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