Three cyclometalated and one coordination compounds [Os(C-N)x(bpy)3-x](m) (x/m=0/2+ (4); 1/1+ (3); 2/1+ (2); 3/0 (1); (-)C-N=2-phenylpyridinato, bpy=2,2'-bipyridine) with drastically different reduction potentials have been used for analyzing the second-order rate constants for one-electron, metal-based osmium(II) to osmium(III) oxidation of the complexes by compound I (k2) and compound II (k3) of horseradish peroxidase. Previously unknown k2 and k3 have been determined by digital simulation of cyclic voltammograms measured in phosphate buffer of pH7.6 and 21 ± 1°C. Osmium(II) species derived from osmium(III) complexes 1 and 2 were generated electrochemically in situ. Under the conditions used the reduction potentials for the Os(III/II) feature equal -0.90, -0.095, 0.23 and 0.85V versus NHE (normal hydrogen electrode) for 1-4, respectively. The rate constants k2 equal ~5 × 10(7), 6 × 10(8), 2 × 10(6) and 1 × 10(5)M(-1)s(-1) and the rate constants k3 equal ~9 × 10(6), 4× 10(7), 1 ×10(6) and 1 × 10(5)M(-1)s(-1) for complexes 1-4, respectively. Both rate constants k2 and k3 first increase with increasing the reaction driving force on going from 4 to 2 but then both decrease on going to complex 1 though the reaction driving force is the highest in this case. The system described has been explored theoretically using docking Monte Carlo simulations.
Keywords: Cyclometalation; Electron transfer; Monte Carlo simulations; Osmium; Peroxidase.
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