DFT as a Powerful Predictive Tool in Photoredox Catalysis: Redox Potentials and Mechanistic Analysis

Abstract

Visible-light photoredox catalysis has come forth as a powerful activation mode in chemical synthesis, affording the development of a multitude of new strategies for molecular construction. However, detailed mechanistic knowledge of the various subprocesses involved is lacking, and new tools for addressing this are needed to drive innovation forward in the area. Herein, we describe predictions of ground- and excited-state redox potentials of ruthenium and iridium photocatalysts using nonrelativistic and scalar relativistic zero-order regular approximation density functional theory (DFT) methods. The computed redox potentials were correlated with experimental values and found to reproduce them well. Relativistic corrections were found to be important to reproduce experimental data. Moreover, the computational protocol allows us to estimate redox potentials that are not currently available in the literature or are difficult to determine experimentally. The mechanistic details of the photocatalyzed C–H funct...