We show the use of arene−chromium tricarbonyl complexesin intra- and intermolecular Pauson−Khand reactions. Bothstyrene and ethynylbenzene complexes react with alkynesand olefins. The synthesis of enynes connected throughchromium-complexed aromatic rings is developed. The intramolecular Pauson−Khand reaction occurs in a totallydiastereoselective manner.