catàlisi homogènia computacional: on érem i on volem anar
TRANSCRIPT
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What did we look like?
Cambridge, 1995 (?)Bellaterra, 1999
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The past of computational homogeneous catalysis
What were
we doing?
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A publication from my doctoral thesis
Heavily simplified molecule
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On a model “reaction”
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Suboptimal computational approach
I Insufficientcomputationalmethod
I “Exotic”optimizationconstraints
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Yet it worked!
Results still validBecause of strong qualitative analysis
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The past of computational homogeneous catalysis
Bottleneck:
Computer power
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The present of computational homogeneous catalysis
What are
we doing?
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Computational homogeneous catalysis in our group
W. M. C. Sameera, Feliu Maseras; WIREs
Comput. Mol. Sci., 2, 375-385 (2012).
Max Garcıa-Melchor, Ataualpa A. C.
Braga, Agustı Lledos, Gregori Ujaque,
Feliu Maseras; Acc. Chem. Res., 46,
2626-2634 (2013).
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Similar, but not the same: two recent examples
I Larger and more complex systems:oxidative coupling
I Microkinetic models on reaction networks: host-guestcatalysis
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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)
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Computed cycle incompatible with experiment:Only CO2 extrusion should be observed!
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Taking explicitly into account the copper species
Opening Pandora’s box
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The key reductive elimination step
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A schematic view of the same transition state
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A mechanism different from conventional reductiveelimination
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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 systemsMaybe in others?
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Similar, but not the same: two recent examples
I Larger and more complex systems:oxidative coupling
I Microkinetic models on reaction networks:host-guest catalysis
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Host-guest catalysis
nanoreactor, nanovessel, capsuleSpecial issue in Chem. Soc. Rev. in 2015
edited by Ballester, P.; Fujita, M.; Rebek, J. Jr.
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A classical example of host-guest catalysis
I W. L. Mock, T. A. Irra, J. P. Wepsiec, T. L. Manimaran; J. Org. Chem., 48,3819-3820 (1983).
I W. L. Mock, T. A. Irra, J. P. Wepsiec, M. Adhya; J. Org. Chem., 54,5302-5308 (1989).
I P. Carlqvist, F. Maseras; Chem. Commun., 748-750 (2007).
I C. Goehry, M. Besora, F. Maseras; ACS Catal., 5, 2445-2451 (2015).
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Initial calculation of catalytic cycle (kcal/mol)
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Complex reaction network: need for a full microkineticmodel
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Evolution of concentrations through time
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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!
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Reality is more complex
I The key barrier is not measured from I but from J
I What do we talk about when discussing reaction acceleration?
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This computed reaction network reproduces all availableexperimental data
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The present of computational homogeneous catalysis
Bottleneck:
Human power
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The future (?) of computational homogeneous catalysis
What do
we want to do?
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Where do we want to go?
I More challenging experimental problems
I Big data treatment
I Descriptors for chemical reactivity
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Challenging problems: water oxidation
I. Funes-Ardoiz, P. Garrido-Barros, A. Llobet, F. Maseras; in preparation
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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/
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Descriptors: statistical treatment of metal-ligand BDE
O. Lakuntza, M. Besora, F. Maseras; in preparation
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People in my group at ICIQ (since 2004)
I Post-doctoralI Peter CarlqvistI Ataualpa BragaI Fabienne BessacI Steven DonaldI Gemma ChristianI Christophe GourlaouenI Maria BesoraI Silvia Dıez-GonzalezI Jesus JoverI Carina BacktorpI Ainara NovaI W. M. C. SameeraI Laura EstevezI Maxime MercyI Oier LakuntzaI Mauro Fianchini
I Graduate studentsI David BalcellsI Alfons Nonell-CanalsI Elena Herrero-GomezI Torstein FjermestadI Abel LocatiI Charles GoehryI Chunhui LiuI Andrey KonovalovI Vıctor Fernandez-AlvarezI Rositha KuniyilI Ignacio Funes-ArdoizI Adiran de AguirreI Angel Mudarra
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Our computational group at ICIQ May ’16