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Thermodynamics of oxygen activation by macrocyclic complexes of rhodium.

Szajna-Fuller E, Bakac A

Ames Laboratory, Iowa State University, Ames, Iowa 50011, USA.

The oxidation of ABTS2- [2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate)] with a superoxorhodium(III) complex, L2(H2O)RhOO2+ (L2 = meso-hexamethylcyclam) is characterized by an acid-dependent equilibrium constant, log(Ke/[H+]) = 4.91 +/- 0.10 in the pH range of 4.89-6.49. This equilibrium constant was used to calculate the reduction potential for the L2(H2O)RhOO2+/L2(H2O)RhOOH2+ couple, E0 = 0.97 V vs NHE. The pH dependence of the kinetics of the L2(H2O)RhOOH2+/I- reaction yielded the acid dissociation constant for the coordinated water in L2(H2O)RhOOH2+, pKa = 6.9. Spectrophotometric pH titrations provided pKa = 6.6 for the superoxo complex, L2(H2O)RhOO2+. The combination of the two pKa values with the reduction potential measured in acidic solutions yielded the reduction potential E0 = 0.95 V for the L2(HO)RhOO+/L2(HO)RhOOH+ couple. Thermochemical calculations yielded the bond-dissociation free energy of the L2(H2O)RhOO-H2+ bond as 315 kJ/mol at 298 K.

Published 6 December 2007 in Inorg Chem, 46(25): 10907-12.
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