High five! The quintuply bonded molybdenum amidinate 1 reacts with two equivalents of 1‐pentyne through a [2+2+2] cycloaddition reaction to give the first examples of the benzannulated product 2. The C4Mo2 rings exhibit aromatic character. Treatment of 1 with internal alkynes afforded the 2:1 and 1:1 [2+2] cycloadducts, which are mechanistically associated with the formation of 2.
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