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Naphthalene and acenaphthene with peri 2‐py and BMes2 (py=pyridyl, Mes=mesityl) substituents have been found to undergo facile phototransformation, cleavage of a C−C bond of naphthalene, and formation of 2‐py‐bound benzoborepins as the major products. Mechanistic pathways of this photoreaction have been established by examination of both excited and ground states by using CASSCF and CASPT2 methods...
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