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‐triphosCy)(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 C1 building blocks.
Herein a highly active non-precious transition metal catalyst for the homogeneous hydrogenation of carbon dioxide to formate is presented. Detailed ligand optimisation enabled the development of a nickel-based catalytic system with exceptional productivity.
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