The reaction of N-toluenesulfonylpyrrole with benzonitrile at room temperature afforded 4-methyl-N-[phenyl(1H-pyrrol-2yl)methylene]toluenesulfonamide (L). The ligand (L) was reacted with selected first, second and third row transition metal salts in low oxidation states, in a basic medium, to afford complexes in different coordination modes ranging from three to five coordinated systems. Complexes of the type NiL2 (2), CuL2 (3), CuL[P(pH3)] (7), AgL[P(pH3)]2 (8), AgL[P(Ph)3] (9), and PtL(COD) (10) with unusual η2,η2 to η2,η1 rearrangement, following double bond migration to form 1,2-η2-σ-cycloocta-1,4-dienyl σ/π coordinating bidentate ligand, were achieved. The reaction of L in the presence of excess DBU afforded a bis-coordinated complexes of the type CoL2(DBU) (4) and ZnL2(DBU) (5). All compounds were structurally characterised by different techniques including 1H and 13C NMR, UV–Vis, IR, Mass spectrometry and elemental analysis. The molecular structures of the ligand L and complexes 4, 7, 8, 9 and 10 were determined by X-ray diffraction analysis. In all metal complexes, L behaved as a bidentate chelating ligand through the sulfonylimine nitrogen and the pyrrole nitrogen. Complexes 6, 8 and 9 exhibited moderate activity against HeLa cell lines, with 8 showing the highest activity with IC50 of 3.6μM, 9 (4.3μM) and 10 (5.43μM).