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Carbon dioxide hydrogenation with base to generate formate salts can provide a means of storing hydrogen in an energy dense solid. However, this application requires catalytic CO2 hydrogenation, which would ideally use an earth abundant metal catalyst. In this article, six new (CNC)CoIL2 pincer complexes were synthesized and fully characterized, including single crystal X-Ray diffraction analysis on four new complexes. These complexes contain an imidazole-based (1R) N-heterocyclic carbene (NHC) ring or a benzimidazole based NHC ring (2R) in the CNC pincer. The R group is para to N on the pyridine ring and been varied from electron withdrawing (CF3) to donating (Me, OMe) substituents. The L type ligands have included CO and phosphine ligands (in PPh32 and PMe32). Thus, two known Co complexes (1, 1OMe) and six new complexes (1Me, 1CF3, 2, 2OMe, PPh32, PMe32) were studied for the CO2 hydrogenation reaction. In general, the unsubstituted CNC pincer complexes bearing two carbonyl ligands led to the highest activity. The best catalyst, 2, remains active for over 16 h and produces a turnover number of 39,800 with 20 bars of 1:1 CO2 / H2 mixture at 60 °C. A computational study of the mechanism of CO2 hydrogenation is also reported. 

The synthesis and the crystal structure of 1 H -imidazole-1-methanol, C 4 H 6 N 2 O, are described. This compound comprises an imidazole ring with a methanol group attached at the 1-position affording an imine nitrogen atom able to receive a hydrogen bond and an alcohol group able to donate to a hydrogen bond. This imidazole methanol crystallizes with monoclinic ( P 2 1 / n ) symmetry with three symmetry-unique molecules. These three molecules are connected via O—H...N hydrogen bonding in a head-to-tail configuration to form independent three-membered macrocycles.