Oxidative Catalysis by TAMLs: Obtaining Rate Constants for Non-Absorbing Targets by UV-Vis Spectroscopy

Abstract

Understanding the catalysis of oxidative reactions by TAML activators of peroxides, i. e. iron(III) complexes of tetraamide macrocyclic ligands, advocated a spectrophotometric procedure for quantifying the catalytic activity of TAMLs for colorless targets (k_II ', M^-1 s^-1 ), which is incomparably more advantageous in terms of time, cost, energy, and ecology than NMR, HPLC, UPLC, GC-MS and other similar techniques. Dyes Orange II or Safranin O (S) are catalytically bleached by non-excessive amount of H₂ O₂ in the presence of colorless substrates (S₁ ) according to the rate law: -d[S]/dt=k_I k_II [H₂ O₂ ][S][TAML]/(k_I [H₂ O₂ ]+k_II [S]+k_II '[S₁ ]). The bleaching rate is thus a descending hyperbolic function of S₁ : v=ab/(b+[S₁ ]). Values of k_II ' found from a and b for phenol and propranolol with commonly used TAML [Fe^III {o,o'-C₆ H₄ (NCONMe₂ CO)₂ CMe₂ }₂ (OH₂ )]⁺ are consistent with those for S₁ (phenol, propranolol) obtained directly by UPLC. The study sends vital messages to enzymologists and environmentalists.

Keywords: TAML activators; kinetics; non-absorbing substrates; rate constants; uv-vis spectroscopy.