journal article
Feb 20, 2009
C−C Reductive Elimination in Palladium Complexes, and the Role of Coupling Additives. A DFT Study Supported by Experiment
Martín Pérez-Rodríguez
Ataualpa A. C. Braga
Max García-Melchor
Mónica H. Pérez-Temprano
Juan A. Casares
Gregori Ujaque
Angel R. de Lera
Rosana Álvarez
Feliu Maseras
Pablo Espinet
Max García-Melchor
Mónica H. Pérez-Temprano
Juan A. Casares
Gregori Ujaque
Angel R. de Lera
Rosana Álvarez
Feliu Maseras
Pablo Espinet
Journal of the American Chemical Society
Vol. 131
No. 10
pp. 3650-3657
·
American Chemical Society (ACS)
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References
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In principle, these equilibria could be analyzed theoretically from the computed ligand dissociation energies, collected inTable SI4of theSupporting Information, but estimation of these specific equilibrium constants with the computational methods applied is troublesome. In fact, the two magnitudes reported, potential energy and free energy, present sharply different values, with differences around 16 kcal/mol. This discrepancy proves the importance of entropic corrections in these bimolecular processes. Unfortunately, in our computational approach, these particular terms are estimated through assumption of ideal gas behavior of the molecules, which is obviously not the optimal choice for systems in solution. Moreover, experimental reactions can be carried out in solvents of very different polarity. Thus, rather than focusing on the intrinsically inaccurate estimation of these equilibrium constants, we decided to analyze the trends in the computed activation barriers associated with the different ligands, where entropic contributions are less critical.
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An additional set of calculations we carried out to check whether the energy barrier to olefin rotation could be relevant to the overall kinetics. In these calculations, collected in theSupporting Information(Figure SI5), we found two local minima forcis-[PdMe2(PMe3)(H2C═CH2)]. The most stable one is the out-of-plane species reported in the text; a secondary in-plane species is 4.7 kcal/mol higher in energy. The transition state between these two minima is only 1.2 kcal/mol above the least stable minimum, indicative of a fast process at room temperature.
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Showing 50 of 60 references
Cited By
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Highly-chemoselective step-down reduction of carboxylic acids to aromatic hydrocarbons via palladium catalysis
Chemical Science
Chengwei Liu, Zhi-Xin Qin · 2019
Metrics
183
Citations
60
References
Details
- Published
- Feb 20, 2009
- Vol/Issue
- 131(10)
- Pages
- 3650-3657
Authors
Cite This Article
Martín Pérez-Rodríguez, Ataualpa A. C. Braga, Max García-Melchor, et al. (2009). C−C Reductive Elimination in Palladium Complexes, and the Role of Coupling Additives. A DFT Study Supported by Experiment. Journal of the American Chemical Society, 131(10), 3650-3657. https://doi.org/10.1021/ja808036j
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