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Activation of Carbon Dioxide by Bicyclic Amidines
Abstract
Activation of the carbon dioxide molecule was achieved using bicyclic amidines (DBU, PMDBD, and DBN). The solution reaction of CO(2) with amidines yielded the corresponding zwitterionic complexes through the formation of a N-CO(2) bond. (13)C NMR data confirmed the carbamic nature of the carbamic zwitterions, DBU-CO(2) and PMDBD-CO(2). However, when these adducts were crystallized, the X-ray analyses of the single crystals were in agreement with bisamidinium bicarbonate salt structures, indicating that structural changes occurred in the crystallization process. The elemental and thermogravimetric analysis data for the carbamic zwitterions, DBU-CO(2) and PMDBD-CO(2), initially obtained by the direct reaction of amidines with CO(2), suggest that these molecules are probably associated with one molecule of water by hydrogen-bond formation (amidinium(+)-COO(-)...H(2)O). A correlation was observed between the thermal stability and the transcarboxylating activity for the amidine-CO(2) complexes. Theoretical calculations of hardness were performed at the B3LYP/cc-pVTZ level of theory and showed concordance with the experimental reactivity of DBU and PMDBD toward CO(2).
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Hori, Y., Wakebe, H., Tsukamoto, T., & Koga, O. (1994) · Electrochimica Acta · doi:10.1016/0013-4686(94)85172-7 · Cited by 2,140
Hori, Y., Kikuchi, K., & Suzuki, S. (1985) · Chemistry Letters · doi:10.1246/cl.1985.1695 · Cited by 1,401
Cited by
Photochemical Reduction of CO2 by Graphitic Carbon Nitride Polymers
Lin, J., Pan, Z., & Wang, X. (2014) · ACS Sustainable Chemistry & Engineering · doi:10.1021/sc4004295 · Cited by 409
Metadata
- Authors
- Pérez, E. R., Santos, R. H. A., Gambardella, M. T. P., de Macedo, L. G. M., Rodrigues-Filho, U. P., Launay, J.-C., & Franco, D. W.
- Venue
- The Journal of Organic Chemistry
- Publisher
- American Chemical Society (ACS)
- Published
- 2004-10-09
- Volume
- 69
- Issue
- 23
- Pages
- 8005-8011
- ISSN
- 0022-3263 (ISSN-L)
- 1520-6904
- OpenAlex
- W2076521037
- Cited by
- 198
- References
- 2
- FWCI
- 4.07
- Type
- journal article
- Language
- en
- Open access
- closed
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- Pérez, E. R., Santos, R. H. A., Gambardella, M. T. P., de Macedo, L. G. M., Rodrigues-Filho, U. P., Launay, J.-C., & Franco, D. W. (2004). Activation of Carbon Dioxide by Bicyclic Amidines. The Journal of Organic Chemistry. https://doi.org/10.1021/jo049243q
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