|This work deals with the reactions of Group 4 metallocene alkyne complexes with various nitriles. The focus lies on the influence of the Cp-ligand, the metal and the structure of the nitrile. Especially in the reactions with aryl nitriles and cyanopyridines highly selective unusual couplings were observed leading in most cases to new five-membered metallacycles. Their reactivity was examined as well. In the reactions with dicyano compounds supramolecular complexes were formed which are considered as potential catalysts.