Herein a non-precious transition-metal catalyst system for the selective synthesis of dialkoxymethane ethers from carbon dioxide and molecular hydrogen is presented. The development of a tailored catalyst system based on cobalt salts in combination with selected Triphos ligands and acidic co-catalysts enabled a synthetic pathway, avoiding the oxidation of methanol to attain the formaldehyde level of the central CH unit. This unprecedented productivity based on the molecular cobalt catalyst is the first example of a non-precious transition-metal system for this transformation utilizing renewable carbon dioxide sources.

The direct hydrogenation of carbon dioxide to methanol represents a challenging transformation for molecular catalyst, and only a few systems facilitate this reaction. Herein, molecular complexes based on the tridentate tdppcy ligand are described, enabling the variable synthesis of structurally tailored catalytic systems. In combination with selected ruthenium precursors and suitable cocatalysts the direct hydrogenation of carbon dioxide could be demonstrated with unprecedented activity. Moreover, the versatile catalyst allowed the reaction in two-phase systems, paving the way to adapted reaction concepts for the utilization of the renewable carbon source carbon dioxide.

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.

A series of [(PMP)Rh(CO)Cl] complexes was synthesised and the impact of the metalloligands Cu, Li and Zn on the CO stretching band was analysed.

Herein an on-precious transition-metal catalyst system for the selective synthesis of dialkoxymethane ethers from carbon dioxide and molecular hydrogen is presented. The development of atailored catalyst system based on cobalt salts in combination with selected Triphos ligands and acidic cocatalysts enabled asynthetic pathway,avoiding the oxidation of methanol to attain the formaldehyde level of the central CH 2 unit. This unprecedented productivity based on the molecular cobalt catalyst is the first example of anon-precious transitionmetal system for this transformation utilizing renewable carbon dioxide sources. Angewandte Chemie Communications