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Photolysis of the cyclic phosphine oligomer [PPh]5 in the presence of pentaarylboroles leads to the formation of 1,2‐phosphaborines by the formal insertion of a phenylphosphinidene fragment into the endocyclic CB bond. The solid‐state structure features a virtually planar central ring with bond lengths indicating significant delocalization. Appreciable ring current in the 1,2‐phosphaborine core,...
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