In situ reaction monitoring is a powerful tool to track reactons in real time under synthetically relevant conditions. Such investgations unveil intermediates and allow to determine rate dependencies to understand reaction kinetics, which is essential to elucidate the underlying mechanism. In this talk, I will present how in situ reaction monitoring was used to provide mechanistic insights in two photocatalytic reactions. First, a comprehensive kinetic examinaton of a dual nickel/photocatalytic C–O arylation using a homogeneous photocatalyst or a heterogeneous photocatalyst will be discussed. We used in situ infrared spectroscopy for in-depth kinetic studies of both catalytic systems. Data processing has been carried out by applying variable time normalization analysis (VTNA). The studies revealed arguments against the current mechanistic hypothesis, which states that the photocatalyst is only involved to trigger reductive eliminaton. Second, I will present our eforts to track a newly developed photo-oxidative cleavage of benzyl ether protecting groups using a LED-NMR setup. These investigations support the underlying mechanistic hypothesis and supports the notion that the reaction ceases upon light removal.

Mechanistic insights through in situ monitoring in photocatalytic synthesis

ACS Spring 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.