Abstract

AbstractThe reactivity of the electronically unsaturated diene complexes (C5Me5)M(2,3‐dimethyl‐1,3‐butadiene)Cl (M = Ti, Hf) with symmetrical acetylenes RCCR (R = H, Me, Ph) is reported. Whereas the reaction of the Hf complex with ethyne resulted in a product derived from initial insertion into the metal‐diene bond, elimination of the diene was observed in the other reactions. Two types of metallacyclo‐2,4‐pentadiene products, formed by oxidative coupling of acetylenes, were isolated: monomeric (C5Me5)Hf(C4Ph4)Cl and dimeric [(C5Me5)TiCl]2(C4Me4).

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