As known from various biological important macrocycles (porphyrines, corrines) the single heterocycle C4H5N is able to form pyrrolyl compounds with a transition metal-to-nitrogen bond. These can be synthesized from metal halides and LiPyrr in ether or THF under anaerobic conditions. Binary and coordination compounds as well as Cp-derivatives of both Ti and Ni, their chemical, magnetic, IR- and PMR-spectroscopic properties are described to confirm the structures