Catàlisi homogènia computacional: on érem i on volem anar
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Computational homogeneous catalysis has progressed from early simplified models to more complex and realistic simulations. Current research involves larger catalytic systems like oxidative coupling reactions and microkinetic models of reaction networks in host-guest catalysis. Two recent examples are discussed: a Rh/Cu oxidative coupling that operates by a cooperative reductive elimination mechanism, and a host-guest catalyzed reaction where acceleration is mostly due to an entropic effect. The future of the field may involve more challenging problems like water oxidation, big data analysis, and statistical studies to develop reactivity descriptors.
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Catàlisi homogènia computacional: on érem i on volem anar
- 2. What did we look like? Cambridge, 1995 (?) Bellaterra, 1999
- 3. The past of computational homogeneous catalysis What were we doing?
- 4. A publication from my doctoral thesis Heavily simplified molecule
- 5. On a model “reaction”
- 6. Suboptimal computational approach Insufficient computational method “Exotic” optimization constraints
- 7. Yet it worked! Results still valid Because of strong qualitative analysis
- 8. The past of computational homogeneous catalysis Bottleneck: Computer power
- 9. The present of computational homogeneous catalysis What are we doing?
- 10. Computational homogeneous catalysis in our group W. M. C. Sameera, Feliu Maseras; WIREs Comput. Mol. Sci., 2, 375-385 (2012). Max Garc´ıa-Melchor, Ataualpa A. C. Braga, Agust´ı Lled´os, Gregori Ujaque, Feliu Maseras; Acc. Chem. Res., 46, 2626-2634 (2013).
- 11. Similar, but not the same: two recent examples Larger and more complex systems: oxidative coupling Microkinetic models on reaction networks: host-guest catalysis
- 12. Oxidative coupling: Miura-Satoh Rh(III)/Cu(II) system K. Ueura, T. Satoh, M. Miura; Org. Lett., 9, 1407 (2007) K. Ueura, T. Satoh, M. Miura; J. Org. Chem., 72, 5362 (2007)
- 13. Computed cycle incompatible with experiment: Only CO2 extrusion should be observed!
- 14. Taking explicitly into account the copper species Opening Pandora’s box
- 15. The key reductive elimination step
- 16. A schematic view of the same transition state
- 17. A mechanism different from conventional reductive elimination
- 18. Cooperative reductive elimination I. Funes-Ardoiz, F. Maseras; Angew. Chem. Int. Ed., 55, 2764-2767 (2016). Likely operating in all Rh(III)/Cu(II) catalytic systems Maybe in others?
- 19. Similar, but not the same: two recent examples Larger and more complex systems: oxidative coupling Microkinetic models on reaction networks: host-guest catalysis
- 20. Host-guest catalysis nanoreactor, nanovessel, capsule Special issue in Chem. Soc. Rev. in 2015 edited by Ballester, P.; Fujita, M.; Rebek, J. Jr.
- 21. A classical example of host-guest catalysis W. L. Mock, T. A. Irra, J. P. Wepsiec, T. L. Manimaran; J. Org. Chem., 48, 3819-3820 (1983). W. L. Mock, T. A. Irra, J. P. Wepsiec, M. Adhya; J. Org. Chem., 54, 5302-5308 (1989). P. Carlqvist, F. Maseras; Chem. Commun., 748-750 (2007). C. Goehry, M. Besora, F. Maseras; ACS Catal., 5, 2445-2451 (2015).
- 22. Initial calculation of catalytic cycle (kcal/mol)
- 23. Complex reaction network: need for a full microkinetic model
- 24. Evolution of concentrations through time
- 25. Origin of acceleration ∆G‡ = ∆H‡ − T∆S‡ 26.1 = 14.6 + 11.5 ∆G‡ = ∆H‡ − T∆S‡ 14.0 = 10.4 + 3.6 It is (mostly) the entropic term!
- 26. Reality is more complex The key barrier is not measured from I but from J What do we talk about when discussing reaction acceleration?
- 27. This computed reaction network reproduces all available experimental data
- 28. The present of computational homogeneous catalysis Bottleneck: Human power
- 29. The future (?) of computational homogeneous catalysis What do we want to do?
- 30. Where do we want to go? More challenging experimental problems Big data treatment Descriptors for chemical reactivity
- 31. Challenging problems: water oxidation I. Funes-Ardoiz, P. Garrido-Barros, A. Llobet, F. Maseras; in preparation
- 32. Big data treatment: ioChem-BD M. Alvarez-Moreno, C. de Graaf, F. Maseras, J. M. Poblet, C. Bo; J. Chem. Inf. Model., 55, 95-103 (2015). http://iochem-bd.org/
- 33. Descriptors: statistical treatment of metal-ligand BDE O. Lakuntza, M. Besora, F. Maseras; in preparation
- 34. People in my group at ICIQ (since 2004) Post-doctoral Peter Carlqvist Ataualpa Braga Fabienne Bessac Steven Donald Gemma Christian Christophe Gourlaouen Maria Besora Silvia D´ıez-Gonz´alez Jes´us Jover Carina B¨acktorp Ainara Nova W. M. C. Sameera Laura Est´evez Maxime Mercy Oier Lakuntza Mauro Fianchini Graduate students David Balcells Alfons Nonell-Canals Elena Herrero-G´omez Torstein Fjermestad Abel Locati Charles Goehry Chunhui Liu Andrey Konovalov V´ıctor Fern´andez-Alvarez Rositha Kuniyil Ignacio Funes-Ardoiz Adiran de Aguirre ´Angel Mudarra
- 35. Our computational group at ICIQ May ’16