Kinetics of Oxidation of a Cuprous 2,2′,2″-Terpyridine Complex by Molecular Oxygen

2,2′,2″-Terpyridine (terpy) has been found to form a bis cuprous complex, Cu(terpy)2+, in aqueous acetonitrile solution. The reaction with molecular oxygen was found to proceed with a two-electron reduction of O2. [formula omitted] The kinetics of this reaction has been studied at 25.0° over the pH range from 5.3 to 8.0, and the rate law found to be -d[Cu(terpy)2⁺]/dt = Kexpti[Cu(terpy)2⁺] [O2], where Kexptl = a + b[CH3CN] + c[CH3CN]²/[terpy]xs, and a = 1.6 × 10⁴ M^-1 sec^-1, b = 4.8 × 10³ M^-2 sec^-1, c = 5.1 × 10^-1 M sec^-1, and [terpy]xs = [terpy]tot-2[Cu⁺], Possible mechanisms for this reaction are discussed. © 1975, American Chemical Society. All rights reserved.

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Author Alvin L. Crumbliss Chemistry