Manganese Catalyzed Hydrogenation of Organic Carbonates to Methanol and Alcohols

• Published in: Angewandte Chemie International Edition Vol. 57; no. 37; pp. 12076 - 12080
• Main Authors: Kumar, Amit, Janes, Trevor, Espinosa‐Jalapa, Noel Angel, Milstein, David
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 10.09.2018; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Alcohol; Alcohols; Carbon dioxide; Carbonates; Catalysis; Catalysts; Chemistry; Chemistry, Multidisciplinary; Hydrogenation; Intermediates; Ligands; Manganese; Metals; Methanol; Physical Sciences; Science & Technology; carbon dioxide; LOW-PRESSURE HYDROGENATION; BICARBONATES; DEFINED IRON CATALYST; CO2; carbonates; hydrogenation; DIOXIDE HYDROGENATION; AMINES; methanol; HOMOGENEOUS CATALYSIS; CYCLIC CARBONATES; PINCER COMPLEX; DERIVATIVES; Manganese
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201806289

The first example of a homogeneous catalyst based on an earth‐abundant metal for the hydrogenation of organic carbonates to methanol and alcohols is reported. Based on the mechanistic investigation, which indicates metal‐ligand cooperation between the manganese center and the N−H group of the pincer ligand, we propose that the hydrogenation of organic carbonates to methanol occurs via formate and aldehyde intermediates. The reaction offers an indirect route for the conversion of CO2 to methanol, which coupled with the use of an earth abundant catalyst, makes the overall process environmentally benign and sustainable. The first example of a homogeneous catalyst based on an earth‐abundant metal for the hydrogenation of organic carbonates to methanol is reported. The reaction is catalyzed by a manganese pincer complex and offers an indirect route to convert CO2 to methanol, making the overall process environmentally benign and sustainable.