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Hydrogenation of Carbon Dioxide Catalyzed by Ruthenium Trimethylphosphine Complexes: The Accelerating Effect of Certain Alcohols and Amines
Abstract
A trace amount of alcohol cocatalyst and a stoichiometric amount of base are required during the hydrogenation of CO(2) to formic acid catalyzed by ruthenium trimethylphosphine complexes. Variation of the choice of alcohol and base causes wide variation in the rate of reaction. Acidic, nonbulky alcohols and triflic acid increase the rate of hydrogenation an order of magnitude above that which can be obtained with traditionally used methanol or water. Similarly, use of DBU rather than NEt(3) increases the rate of reaction by an order of magnitude. Turnover frequencies up to 95,000 h(-1) have now been obtained, and even higher rates should be possible using the cocatalyst and amine combinations identified herein. Preliminary in situ NMR spectroscopic observations are described, and the possible roles of the alcohol and base are discussed.
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Cited by
Recent advances in catalytic hydrogenation of carbon dioxide
Wang, W., Wang, S., Ma, X., & Gong, J. (2011) · Chemical Society Reviews · doi:10.1039/c1cs15008a · Cited by 3,316
Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO 2 Fixation
Appel, A. M., Bercaw, J. E., Bocarsly, A. B., Dobbek, H., DuBois, D. L., Dupuis, M., Ferry, J. G., Fujita, E., Hille, R., Kenis, P. J. A., et al. (2013) · Chemical Reviews · doi:10.1021/cr300463y · Cited by 2,193
Clapham, S. E., Hadzovic, A., & Morris, R. H. (2004) · Coordination Chemistry Reviews · doi:10.1016/j.ccr.2004.04.007 · Cited by 1,316
Klankermayer, J., Wesselbaum, S., Beydoun, K., & Leitner, W. (2016) · Angewandte Chemie International Edition · doi:10.1002/anie.201507458 · Cited by 856
Dyson, P. J., & Jessop, P. G. (2016) · Catalysis Science & Technology · doi:10.1039/c5cy02197a · Cited by 382
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Metadata
- Authors
- Munshi, P., Main, A. D., Linehan, J. C., Tai, C.-C., & Jessop, P. G.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2002-06-13
- Volume
- 124
- Issue
- 27
- Pages
- 7963-7971
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2021749372
- Cited by
- 346
- References
- 0
- FWCI
- 10.52
- Type
- journal article
- Language
- en
- Open access
- closed
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- Munshi, P., Main, A. D., Linehan, J. C., Tai, C.-C., & Jessop, P. G. (2002). Hydrogenation of Carbon Dioxide Catalyzed by Ruthenium Trimethylphosphine Complexes: The Accelerating Effect of Certain Alcohols and Amines. Journal of the American Chemical Society. https://doi.org/10.1021/ja0167856
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