LAUSR

"Enthalpy-Entropy Compensation Effect" (EECE) is ubiquitous in chemical reactions; however, such an EECE has been rarely explored in biomimetic oxidation reactions. In this study, six manganese(IV)-oxo complexes bearing electron-rich and -deficient porphyrins are synthesized and investigated in various oxidation reactions, such as hydrogen atom transfer (HAT), oxygen atom transfer (OAT), and electron-transfer (ET) reactions. First, all of the six Mn(IV)-oxo porphyrins are highly reactive in the HAT, OAT, and ET reactions. Interestingly, we have observed a reversed reactivity in the HAT and OAT reactions by the electron-rich and -deficient Mn(IV)-oxo porphyrins, depending on reaction temperatures, but not in the ET reactions; the electron-rich Mn(IV)-oxo porphyrins are more reactive than the electron-deficient Mn(IV)-oxo porphyrins at high temperature (e.g., 0 °C), whereas at low temperature (e.g., -60 °C), the electron-deficient Mn(IV)-oxo porphyrins are more reactive than the electron-rich Mn(IV)-oxo porphyrins. Such a reversed reactivity between the electron-rich and -deficient Mn(IV)-oxo porphyrins depending on reaction temperatures is rationalized with EECE; that is, the lower is the activation enthalpy, the more negative is the activation entropy, and vice versa. Interestingly, a unified linear correlation between the activation enthalpies and the activation entropies is observed in the HAT and OAT reactions of the Mn(IV)-oxo porphyrins. Moreover, from the previously reported HAT reactions of nonheme Fe(IV)-oxo complexes, a linear correlation between the activation enthalpies and the activation entropies is also observed. To the best of our knowledge, we report the first detailed mechanistic study of EECE in the oxidation reactions by synthetic high-valent metal-oxo complexes.