Sustainable catalysis with fluxional acridine-based PNP pincer complexes

Abstract

Because of the widespread use of fossil fuels and the resulting global warming, development of sustainable catalytic transformations is now more important than ever to obtain our desired fuels and building materials with the least carbon footprint and waste production. Many sustainable (de)hydrogenation reactions, including CO₂ reduction, H₂ carrier systems, and others, have been reported using molecular pincer complexes. A specific subset of pincer complexes containing a central acridine donor with flanking CH₂PR₂ ligands, known as acridine-based PNP pincer complexes, exhibit special reactivities that are not imitable by other PNP pincer complexes such as pyridine-based or (R₂PCH₂CH₂)₂NH type ligands. The goal of this article is to highlight the unique reactivities of acridine-based complexes and then investigate how these reactivities allow these complexes to catalyse many sustainable reactions that traditional pincer complexes cannot catalyse. To that end, we will initially go over the synthesis and structural features of acridine complexes, such as the labile coordination of the central N donor and the observed fac–mer fluxionality. Following that, distinct reactivity patterns of acridine-based complexes including their reactivity with acids and water will be discussed. Finally, we will discuss the reaction systems that have been developed with acridine complexes thus far, including the notable selective transformations of primary alcohols to primary amines using ammonia, N-heteroaromatic synthesis from alcohols and ammonia, oxidation reactions with water with H₂ liberation, development of H₂ carrier systems, and others, and conclude the article with future possible directions. We hope that the systemic study presented here will aid researchers in developing further sustainable reactions based on the unique acridine-based pincer complexes.