Catalytic (de)hydrogenation promoted by non-precious metals – Co, Fe and Mn: recent advances in an emerging field

Abstract

Catalytic hydrogenation and dehydrogenation reactions form the core of the modern chemical industry. This vast class of reactions is found in any part of chemical synthesis starting from the milligram-scale exploratory organic chemistry to the multi-ton base chemicals production. Noble metal catalysis has long been the key driving force in enabling these transformations with carbonyl substrates and their nitrogen-containing counterparts. This review is aimed at introducing the reader to the remarkable progress made in the last three years in the development of base metal catalysts for hydrogenations and dehydrogenative transformations.

Biomimetic Hydrogenation Catalyzed by a Manganese Model of [Fe]‐Hydrogenase

“…While the activity and scope of 5 in hydrogenation are the best among model complexes of [Fe]‐hydrogenase, they are below those of the most active base metal catalysts for common organic substrates –. We considered that the strength of a biomimetic catalyst like 5 might be its propensity to catalyze biomimetic reactions uncommon to synthetic chemistry.…”

Manganese(III) Porphyrin‐Catalyzed Dehydrogenation of Alcohols to form Imines, Tertiary Amines and Quinolines

“…In fact, the first manganese complex was presented in 2016 and since then many manganese‐based catalysts have been developed for both the dehydrogenation– and the reverse hydrogenation reaction –. With one exception, although, they are all manganese(I) complexes stabilized by CO ligands which are not inexpensive since they are prepared from the costly carbonyl complex Mn 2 (CO) 10 .…”

Synthesis and characterization of bis- and tris-carbonyl Mn(I) and Re(I) PNP pincer complexes

“…In recent years, manganese pincer complexes, where the metal centers adopt a formal oxidation state of +I, have received considerable importance in the field of homogeneous catalysis [1–6]. In comparison to manganese, rhenium pincer complexes remained comparatively unexplored until very recently but are becoming increasingly important as catalysts for hydrogenation/dehydrogenation reactions [7–10].…”