Insertion of Molecular Oxygen into a Gold(III)-Hydride Bond.

The use of molecular oxygen as an oxidant in chemical synthesis has significant environmental and economic benefits, and it is widely used as such in large-scale industrial processes. However, its adoption in highly selective homogeneous catalytic transformations, particularly to produce oxygenated organics, has been hindered by our limited understanding of the mechanisms by which O reacts with transition metals. Of particular relevance are the mechanisms of the reactions of oxygen with late transition metal hydrides as these metal centers are better poised to release oxygenated products.

Thermodynamic Analysis of Metal-Ligand Cooperativity of PNP Ru Complexes: Implications for CO Hydrogenation to Methanol and Catalyst Inhibition.

The hydrogenation of CO in the presence of amines to formate, formamides, and methanol (MeOH) is a promising approach to streamlining carbon capture and recycling. To achieve this, understanding how catalyst design impacts selectivity and performance is critical. Herein we describe a thorough thermochemical analysis of the (de)hydrogenation catalyst, (PNP = 2,6-bis(di--butylphosphinomethyl)pyridine; Ru = Ru(CO)(H)) and correlate our findings to catalyst performance.