Observing the Entry Events of a Titanium‐Based Photoredox Catalytic Cycle in Real Time

Titanium-based catalysis in single electron transfer (SET) steps has evolved into a versatile approach for the synthesis of fine chemicals and first attempts have recently been made to enhance its sustainability by merging it with photo-redox (PR) catalysis. Here, we explore the photochemical principles of all-Ti-based SET-PR-catalysis, i.e. in the absence of a precious metal PR-co-catalyst. By combining time-resolved emission with ultraviolet-pump/mid-infrared-probe (UV/MIR) spectroscopy on femtosecond-to-microsecond time scales we quantify the dynamics of the critical events of entry into the catalytic cycle; namely, the singlet-triplet interconversion of the do-it-all titanocene(IV) PR-catalyst and its one-electron reduction by a sacrificial amine electron donor. The results highlight the importance of the PR-catalyst's singlet-triplet gap as a design guide for future improvements.