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Hydrogenation of CO2 to Formic Acid with a Highly Active Ruthenium Acriphos Complex in DMSO and DMSO/Water

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Haenel,  Matthias
Research Group Haenel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Leitner,  Walter
Makromolekulare Chemie, Lehrstuhl für Technische Chemie und Petrolchemie, RWTH Aachen University, Aachen, Germany;
Research Group Leitner, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Rohmann, K., Kothe, J., Haenel, M., Englert, U., Hölscher, M., & Leitner, W. (2016). Hydrogenation of CO2 to Formic Acid with a Highly Active Ruthenium Acriphos Complex in DMSO and DMSO/Water. Angewandte Chemie International Edition, 55(31), 8966-8969. doi:10.1002/anie.201603878.


Cite as: http://hdl.handle.net/11858/00-001M-0000-002B-9C2F-0
Abstract
The novel [Ru(Acriphos)(PPh3)(Cl)(PhCO2)] [1; Acriphos=4,5-bis(diphenylphosphino)acridine] is an excellent precatalyst for the hydrogenation of CO2 to give formic acid in dimethyl sulfoxide (DMSO) and DMSO/H2O without the need for amine bases as co-reagents. Turnover numbers (TONs) of up to 4200 and turnover frequencies (TOFs) of up to 260 h−1 were achieved, thus rendering 1 one of the most active catalysts for CO2 hydrogenations under additive-free conditions reported to date. The thermodynamic stabilization of the reaction product by the reaction medium, through hydrogen bonds between formic acid and clusters of solvent or water, were rationalized by DFT calculations. The relatively low final concentration of formic acid obtained experimentally under catalytic conditions (0.33 mol L−1) was shown to be limited by product-dependent catalyst inhibition rather than thermodynamic limits, and could be overcome by addition of small amounts of acetate buffer, thus leading to a maximum concentration of free formic acid of 1.27 mol L−1, which corresponds to optimized values of TON=16×103 and TOFavg≈103 h−1.