Thermodynamic Analysis of Metal-Ligand Cooperativity of PNP Ru Complexes: Implications for CO2 Hydrogenation to Methanol and Catalyst Inhibition.

Journal of the American Chemical Society
Cheryl L MathisCaroline T Saouma

Abstract

The hydrogenation of CO2 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)Ru-Cl (PNP = 2,6-bis(di-tert-butylphosphinomethyl)pyridine; Ru = Ru(CO)(H)) and correlate our findings to catalyst performance. Although this catalyst is known to hydrogenate CO2 to formate with a mild base, we show that MeOH is produced when using a strong base. Consistent with pKa measurements, the requirement for a strong base suggests that the deprotonation of a six-coordinate Ru species is integral to the catalytic cycle that produces MeOH. Our studies also indicate that the concentration of MeOH produced is independent of catalyst concentration, consistent with a deactivation pathway that is dependent on methanol concentration, not equivalency. Our temperature-dependent equilibrium studies of the dearomatized congener, (*PNP)Ru, with various H-X species (to give (PNP)Ru-X; X = H, OH, OMe, OCHO, OC(O)NMe2) reveal that formic acid equilibrium is approximately temperature-...Continue Reading

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Citations

Oct 2, 2020·Chemical Communications : Chem Comm·Fang WangCaroline T Saouma
Aug 14, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Giulio BrescianiFabio Marchetti
Nov 26, 2020·Chemistry : a European Journal·Abhishek KumarJoyanta Choudhury
Jul 25, 2020·Journal of the American Chemical Society·Amit KumarDavid Milstein
Aug 5, 2021·The Journal of Physical Chemistry Letters·Chuan-Kai TangYirong Mo
Oct 20, 2021·Journal of the American Chemical Society·Francesca ArcudiEmily A Weiss

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