Combining Experimental Reaction Development with Quantum Chemistry and Machine Learning

Photoredox catalysis has emerged as an alternative to classical cross-coupling reactions, promoting new reactivities. Recently, the use of widely abundant alcohols and aryl bromides as coupling reagents was demonstrated to promote efficient coupling through the Ir/Ni dual photoredox catalytic cycle. However, the mechanism underlying this transformation is still unexplored, and here we report a comprehensive computational study of the catalytic cycle. We have shown that nickel catalysts can promote this reactivity very efficiently through DFT calculations. Two different mechanistic scenarios were explored, suggesting that two catalytic cycles operate simultaneously depending on the concentration of the alkyl radical. Full article

The irradiation of 2-aryl-4-(E-3′-aryl-allylidene)-5(4H)-oxazolones 1 with blue light (456 nm) in the presence of [Ru(bpy)₃](BF₄)₂ (bpy = 2,2′-bipyridine, 5% mol) gives the unstable cyclobutane-bis(oxazolones) 2 by [2+2]-photocycloaddition of two oxazolones 1. Each oxazolone contributes to the formation of 2 with a different C=C bond, one of them reacting through the exocyclic C=C bond, while the other does so through the styryl group. Treatment of unstable cyclobutanes 2 with NaOMe/MeOH produces the oxazolone ring opening reaction, affording stable styryl-cyclobutane bis(amino acids) 3. The reaction starts with formation of the T₁ excited state of the photosensitizer ³[Ru*(bpy)₃]²⁺, which reacts with S₀ of oxazolones 1 through energy transfer to give the oxazolone T₁ state ³(oxa*)-1, which is the reactive species and was characterized by transient absorption spectroscopy. Measurement of the half-life of ³(oxa*)-1 for 1a, 1b and 1d shows large values for 1a and 1b (10–12 μs), while that of 1d is shorter (726 ns). Density functional theory (DFT) modeling displays strong structural differences in the T₁ states of the three oxazolones. Moreover, study of the spin density of T₁ state ³(oxa*)-1 provides clues to understanding the different reactivity of 4-allylidene-oxazolones described here with respect to the previously reported 4-arylidene-oxazolones. Full article

Organic peroxy radicals (RO₂) as key intermediates in tropospheric chemistry exert a controlling influence on the cycling of atmospheric reactive radicals and the production of secondary pollutants, such as ozone and secondary organic aerosols (SOA). Herein, we present a comprehensive study of the self-reaction of ethyl peroxy radicals (C₂H₅O₂) by using advanced vacuum ultraviolet (VUV) photoionization mass spectrometry in combination with theoretical calculations. A VUV discharge lamp in Hefei and synchrotron radiation at the Swiss Light Source (SLS) are employed as the photoionization light sources, combined with a microwave discharge fast flow reactor in Hefei and a laser photolysis reactor at the SLS. The dimeric product, C₂H₅OOC₂H₅, as well as other products, CH₃CHO, C₂H₅OH and C₂H₅O, formed from the self-reaction of C₂H₅O₂ are clearly observed in the photoionization mass spectra. Two kinds of kinetic experiments have been performed in Hefei by either changing the reaction time or the initial concentration of C₂H₅O₂ radicals to confirm the origins of the products and to validate the reaction mechanisms. Based on the fitting of the kinetic data with the theoretically calculated results and the peak area ratios in the photoionization mass spectra, a branching ratio of 10 ± 5% for the pathway leading to the dimeric product C₂H₅OOC₂H₅ is measured. In addition, the adiabatic ionization energy (AIE) of C₂H₅OOC₂H₅ is determined at 8.75 ± 0.05 eV in the photoionization spectrum with the aid of Franck-Condon calculations and its structure is revealed here for the first time. The potential energy surface of the C₂H₅O₂ self-reaction has also been theoretically calculated with a high-level of theory to understand the reaction processes in detail. This study provides a new insight into the direct measurement of the elusive dimeric product ROOR and demonstrates its non-negligible branching ratio in the self-reaction of small RO₂ radicals. Full article