Abstract
The rearrangement of chromium(0) carbene complexes 4 to isocyanides 5 occurs either thermally or by SiO2 catalysis through 1,2-diaminobenzene addition followed by breakage of the bicyclic carbene intermediate 11. Complexes 4 with 1,8-diaminonaphthalene lead in very smooth conditions to 2-substituted perimidines 9 with good yields through an unprecedented cleavage of the carbon skeleton of the metal complex in a formal retro-Aumann reaction.
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