Reactions of N-aryliminopyrrolyl ligand 1a, 2-(2,6- iPr 2C 6H 3N=CH)-C 4H 3NH (Imp Dipp-H), with dibenzylcalcium gave two types of pyrrolylcalcium complexes, bis(iminopyrrolyl)calcium (2a) and (amidopyrrolyl)calcium (3a), via alkane elimination and ligand alkylation reaction, respectively. Preparation of a mono(iminopyrrolyl) complex, (iminopyrrolyl)Ca[N(SiMe 3) 2](THF) 2 (4a), was accomplished by the addition of 1 equiv of 1a to Ca[N(SiMe 3) 2] 2(THF) 2. A series of group 2 metal bis(iminopyrrolyl) complexes, [(Imp Dipp) 2M(THF) 3] (M = Sr (5a), Ba, (6a)) and [(Imp Me) 2Ca(THF) 2] (2b) (2-(4-MeC 6H 4N=CCH 3)-C 4H 3NH (Imp Me-H)), was selectively prepared via amine elimination reactions, and their molecular structures were clarified by X-ray diffraction studies. © 2012 American Chemical Society.