Thermodynamic and Kinetic Aspects of Two- and Three-Electron Redox Processes Mediated by Nitrogen Atom Transfer
Hays, J. Alan
Treatment of (meso-tetra-p-tolylporphyrinato)manganese(V) nitride, (TTP)Mn==N, with (octaethylporphyrinato) manganese(II), Mn(OEP), in toluene leads to the reversible transfer of the nitrido ligand between the two metal complexes to form (OEP)Mn Nand Mn(TTP). The net result is a formal three-electron reduction of (TTP)MnvN to (TTP)Mn11• This occurs with a second-order rate constant of (5.6 ± 1.2) X 103 M-1 s-1 to form an equilibrium mixture with K~ = 1.2 ± 0.5 at 20 °C. The thermodynamic and activation parameters for this process are t:.H0 = 2.0 ± 0.2 kcalfmol, t:.S = 7 .I ± 0.6 calfmol·K, t:.H* = 9.4 ± 0.7 kcal/mol, and t:.S* = -10 ± 2 cal/mol·K. In THF at 20 °C, the equilibrium constant is 1.8 ± 0.2 and the rate constant drops to 2.3 ± 0.3 M-1 s-1• When a manganese(III) porphyrin complex is used as a reductant, reversible nitrogen atom transfer still occurs but mediates a formal two-electron process. At 22 °C, the exchange process between (TTP)MnCI and (OEP)Mn==N produces (TTP)Mn==N and (OEP)MnCI with a second-order rate constant of 0.010 ± 0.007 M-1 s-1 (t:.H* = 19 ± 2 kcal/mol and t:.S* = -3 ± 6 cal/mol·K) and forms an equilibrium mixture with Keq = 24.3 ± 3.3 (t:.H 0 = -7.0 ± 0.6 kcal/mol and t:.S 0 = -17 ± 2 cal/mol·K). Evidence for the formation of a binuclear wnitrido intermediate is presented for both processes. For the two-electron redox reaction, kinetic studies and mechanistic probes support a pathway which involves an initial chloride dissociation from the Mn(III) complex. Nitrogen atom transfer subsequently occurs between the Mn==N complex and the four-coordinate Mn(III) cationic species.
Reprinted (adapted) with permission from Journal of the American Chemical Society 113 (1991): 8478, doi:10.1021/ja00022a040. Copyright 1991 American Chemical Society.