We report the highly chemo-selective catalytic addition of N–H bonds from various aromatic amines to carbodiimides and isocyanates using (Ar-BIAO)ZnCl2 complexes [Ar-BIAO = N-(aryl)imino-acenapthenone, Ar = 2,6-Me2C6H3 (1), 2,4,6 Me3C6H2 (2), 2,6-iPr2C6H3 (3)] as the pre-catalyst to prepare guanidine and urea derivatives in 55-90% yield. The complex 3 showed higher catalytic activity than analogous complexes 1 and 2 under similar reaction conditions. The catalytic guanylation of N–H bonds with heterocumulenes displays a broad substrate scope. The amines having electron donating groups underwent higher conversion than the amines having electron withdrawing groups to afford corresponding guanidine or urea derivatives. A possible mechanism involving penta-coordinated zinc transition state for the catalytic reaction is presented. [Figure not available: see fulltext.] © 2016, Indian Academy of Sciences.