Two new salicylaldiminato-copper(II) complexes, [Cu(L¹)₂] (1) and [Cu(L²)₂] (2) (where HL¹= 4-tert-Butyl-2-[(thiophen-2-ylmethylimino)-methyl]-phenol and HL ²=2, 4-Di-tert-butyl-6-[(thiophen-2-ylmethylimino)-methyl]-phenol), endowed with a pendant thiophenyl moiety, were synthesized and characterized using standard spectroscopic techniques (FT-IR, UV-Vis, MS) and elemental analysis. Complexes 1 and 2 were unequivocally characterized by single crystal X-ray crystallography, which confirmed bidentate bis-chelation of the deprotonated -L¹ and -L² ligands to the copper (II) centres via the phenoxoand imine atoms forming square planar complexes. The copper(II)-hydroperoxo derivatives of 1 and 2 ([(L¹)₂Cu^II-OOH] (3) and [(L²)₂Cu^II -OOH] (4)) were also synthesized and the formation of the active intermediate in solution studied. Complexes 1 and 2 were tested as catalyst precursors in cyclohexane oxidationunder mild reaction conditions using hydrogen peroxide (H₂O₂) as a terminal oxidant, and were found to catalyse oxidation of the substrate with yields comparable to similar mononuclear and even multinuclear copper complexes.