A series of half-sandwich pentamethylcyclopentadienyl chromium (III) complexes bearing a salicylaldiminato ligand, Cp*[2-R1-4-R2-6-(CHNR3) C6H2O] CrCl [R1= iPr (1, 4), tBu (2, 3, 5), Ad (6); R2= H (1, 2, 3), tBu (4, 5, 6); R3= iPr (1, 2, 5, 6), tBu (3, 4)], were synthesized. All complexes were characterized by elemental analyses and the structures of complexes 1–4 and 6 were determined by X-ray diffraction analysis. These complexes adopt a pseudo- ...