Base‐Free Hydrogenation of Carbon Dioxide to Methyl Formate with a Molecular Ruthenium‐Phosphine Catalyst

Abstract

Abstract Herein, a molecular ruthenium‐phosphine catalyst system for the effective base‐free methyl formate production from carbon dioxide is described. In detail, the novel [Ru(N‐triphos Cy )(tmm)] complex, bearing sterically demanding cyclohexyl groups in the triphos‐ligand structure, enabled in combination with the Lewis acid Al(OTf) 3 the selective transformation of carbon dioxide to methyl formate with unprecedented activity. From a mechanistic perspective, in the initial step formic acid is formed, undergoing a consecutive Lewis acid promoted esterification with methanol to methyl formate. This selective transformation with carbon dioxide paves the way to versatile processes for important C 1 building blocks.