A Chiral Titanocene Complex as Regiodivergent Photoredox Catalyst: Synthetic Scope and Mechanism of Catalyst Generation.

We describe a combined synthetic, spectroscopic, and computational study of a chiral titanocene complex as a regiodivergent photoredox catalyst (PRC). With Kagan's complex catCl2 either monoprotected 1,3-diols or 1,4-diols can be obtained in high selectivity from a common epoxide substrate in a regiodivergent epoxide opening depending on which enantiomer of the catalyst is employed. Due to the catalyst-controlled regioselectivity of ring opening and the broader substrate scope, the PRC with catCl2 is also a highly attractive branching point for diversity-oriented synthesis. The photochemical processes of cat(NCS)2, a suitable model for catCl2, were probed by time-correlated single-photon counting. The photoexcited complex displays a thermally activated delayed fluorescence as a result of a singlet-triplet equilibration, S1 ⇄ T1, via intersystem crossing and recrossing. Its triplet state is quenched by electron transfer to the T1 state. Computational and cyclic voltammetry studies highlight the importance of our sulfonamide additive. By bonding to sulfonamide additives, chloride abstraction from [catCl2]- is facilitated, and catalyst deactivation by coordination of the sulfonamide group is circumvented.

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.