Efficient hydrogenation of organic carbonates, carbamates and formates indicates alternative routes to methanol based on CO2 and CO

• Published in: Nature chemistry 2011-07, Vol.3 (8), p.609-614
• Main Authors: Balaraman, Ekambaram, Gunanathan, Chidambaram, Zhang, Jing, Shimon, Linda J. W., Milstein, David
• Format: Article
• Language: English
• Subjects: 639/638/224; 639/638/263/406/77; Alcohol; Alcohols; Amines; Analytical Chemistry; Biochemistry; Carbamates (tradename); Carbamates - chemistry; Carbon dioxide; Carbon Dioxide - chemistry; Carbon monoxide; Carbon Monoxide - chemistry; Carbonates; Carbonic Acid - chemistry; Catalysis; Chemistry; Chemistry/Food Science; Cooperation; Formates; Formates - chemistry; Hydrogen - chemistry; Hydrogen storage; Hydrogenation; Inorganic Chemistry; Ligands; Methanol; Methanol - chemistry; Models, Molecular; Organic Chemistry; Physical Chemistry; Pyridines; Solvents; X-Ray Diffraction
• ISSN: 1755-4330; 1755-4349
• DOI: 10.1038/nchem.1089

Catalytic hydrogenation of organic carbonates, carbamates and formates is of significant interest both conceptually and practically, because these compounds can be produced from CO 2 and CO, and their mild hydrogenation can provide alternative, mild approaches to the indirect hydrogenation of CO 2 and CO to methanol, an important fuel and synthetic building block. Here, we report for the first time catalytic hydrogenation of organic carbonates to alcohols, and carbamates to alcohols and amines. Unprecedented homogeneously catalysed hydrogenation of organic formates to methanol has also been accomplished. The reactions are efficiently catalysed by dearomatized PNN Ru( II ) pincer complexes derived from pyridine- and bipyridine-based tridentate ligands. These atom-economical reactions proceed under neutral, homogeneous conditions, at mild temperatures and under mild hydrogen pressures, and can operate in the absence of solvent with no generation of waste, representing the ultimate ‘green’ reactions. A possible mechanism involves metal–ligand cooperation by aromatization–dearomatization of the heteroaromatic pincer core. Producing methanol — useful as both a fuel and a synthetic building block — from carbon monoxide and carbon dioxide has been achieved using homogeneous catalytic hydrogenation of carbonates, carbamates and formates. The catalyst is a dearomatized ruthenium( II ) pincer complex and the reaction proceeds efficiently under mild conditions.