Several palladacycle and platinacycle complexes have been prepared from easily available or naturally occurring indole derivatives, such as gramine and related compounds. Dimeric complexes were obtained with Pd(OAc) 2 , while Pt(DMSO) 2 Cl 2 mainly afforded monomeric structures. A notable feature of these reactions was the formation of new M–C bonds between Pd or Pt and C-2 and C-3 of the indole ring. With ligands like 2-(2′-pyridyl)-1H-indoles, N–N metallacycles were generated instead: in fact new C–M bonds with the C-3 position could only form if N-substituted indoles were used. The reactivity of Pd dimeric complexes with PPh 3 , sym-collidine and DMAP was explored to obtain monomeric complexes. Three such compounds were prepared, one of which was characterized by X-ray diffraction. Metathetical reactions were carried out to effect a ligand exchange replacing OAc with halide ions, with the aim to synthesize μ-Cl and μ-Br bridged structures. Turning to the synthesis of hetaryl complexes, functionalization of the C-2 position on the indole ring was achieved. These complexes were prepared by substitution reactions starting from gramine and/or its alkylammonium salts.