The difference bidirectionality makes to the kinetic modeling of molecular catalysis

Abstract

The quantitative modeling of voltammograms obtained with molecular redox catalysts is important for mechanistic studies and benchmarking. Most kinetic models developed for that purpose were based on unidirectional reaction mechanisms, but many redox enzymes work in both directions of the reaction, and chemists have recently successfully designed bidirectional, synthetic, molecular catalysts. An important conclusion from recent work is that unidirectional kinetic models should not be used to interpret bidirectional electrochemical responses. Understanding the latter will require much more work than simply adapting unidirectional models.