Photoredox-HAT Catalysis for Primary Amine α-C-H Alkylation: Mechanistic Insight with Transient Absorption Spectroscopy.

The synergistic use of (organo)photoredox catalysts with hydrogen-atom transfer (HAT) cocatalysts has emerged as a powerful strategy for innate C(sp3)-H bond functionalization, particularly for C-H bonds α- to nitrogen. Azide ion (N3-) was recently identified as an effective HAT catalyst for the challenging α-C-H alkylation of unprotected, primary alkylamines, in combination with dicyanoarene photocatalysts such as 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN). Here, time-resolved transient absorption spectroscopy over sub-picosecond to microsecond timescales provides kinetic and mechanistic details of the photoredox catalytic cycle in acetonitrile solution. Direct observation of the electron transfer from N3- to photoexcited 4CzIPN reveals the participation of the S1 excited electronic state of the organic photocatalyst as an electron acceptor, but the N3• radical product of this reaction is not observed. Instead, both time-resolved infrared and UV-visible spectroscopic measurements implicate rapid association of N3• with N3- (a favorable process in acetonitrile) to form the N6•- radical anion. Electronic structure calculations indicate that N3• is the active participant in the HAT reaction, suggesting a role for N6•- as a reservoir that regulates the concentration of N3•.

Transient absorption spectroscopy of the electron transfer step in the photochemically activated polymerizations of N-ethylcarbazole and 9-phenylcarbazole.

The polymerization of photoexcited N-ethylcarbazole (N-EC) in the presence of an electron acceptor begins with an electron transfer (ET) step to generate a radical cation of N-EC (N-EC˙+). Here, the production of N-EC˙+ is studied on picosecond to nanosecond timescales after N-EC photoexcitation at a wavelength λex = 345 nm using transient electronic and vibrational absorption spectroscopy. The kinetics and mechanisms of ET to diphenyliodonium hexafluorophosphate (Ph2I+PF6-) or para-alkylated variants are examined in dichloromethane (DCM) and acetonitrile (ACN) solutions. The generation of N-EC˙+ is well described by a diffusional kinetic model based on Smoluchowski theory: with Ph2I+PF6-, the derived bimolecular rate coefficient for ET is kET = (1.8 ± 0.5) × 1010 M-1 s-1 in DCM, which is consistent with diffusion-limited kinetics. This ET occurs from the first excited singlet (S1) state of N-EC, in competition with intersystem crossing to populate the triplet (T1) state, from which ET may also arise. A faster component of the ET reaction suggests pre-formation of a ground-state complex between N-EC and the electron acceptor. In ACN, the contribution from pre-reaction complexes is smaller, and the derived ET rate coefficient is kET = (1.0 ± 0.3) × 1010 M-1 s-1. Corresponding measurements for solutions of photoexcited 9-phenylcarbazole (9-PC) and Ph2I+PF6- give kET = (5 ± 1) × 109 M-1 s-1 in DCM. Structural modifications of the electron acceptor to increase its steric bulk reduce the magnitude of kET: methyl and t-butyl additions to the para positions of the phenyl rings (para Me2Ph2I+PF6- and t-butyl-Ph2I+PF6-) respectively give kET = (1.2 ± 0.3) × 1010 M-1 s-1 and kET = (5.4 ± 1.5) × 109 M-1 s-1 for reaction with photoexcited N-EC in DCM. These reductions in kET are attributed to slower rates of diffusion or to steric constraints in the ET reaction.