DESIGN OF NOVEL CATALYTIC SYSTEMS FOR DEHYDROGENATION OF FORMIC ACID /HYDROGENATION OF CARBON DIOXIDE

In recent years, metal complexes, in which both the metal center and the ligand play active and cooperative roles, have emerged as very promising catalysts, capable of activating and forming chemical bonds through non-oxidative pathways alternative to the classical oxidative addition/reductive elimination sequence. The key mechanistic steps usually include a reversible switching between the coordination modes of the ligands that are bound to the catalytically active metal center.

In the current research we wish to shed light on the synthesis, characterization, and proprieties of new series of three-dimensional cooperative PC(sp³)P pincer-like complexes based on dibenzobarrelene backbone, and their ability of promoting a variety of catalytic transformations through the unprecedented ligand-metal cooperating mechanism. In particular, we wish to describe the rational design of iridium PC(sp³)P-pincer catalytic systems for dehydrogenation of formic acid/hydrogenation of carbon dioxide and in the development of new generic transformations involving structural modification of functionalized hydrocarbon substrates using formic acid as a source of H₂ and CO₂. This goal was motivated by the economic and ecological sustainability of formic acid, as well as by importance of fundamental understanding of the carbon dioxide interactions with transition metal catalysts.

The new catalysts demonstrated very high activity in the of dehydrogenation of formic acid and hydrogenation of carbon dioxide reactions, relevant in hydrogen production.