What did we look like?

Cambridge, 1995 (?)Bellaterra, 1999

The past of computational homogeneous catalysis

What were

we doing?

A publication from my doctoral thesis

Heavily simplified molecule

On a model “reaction”

Suboptimal computational approach

I Insufficientcomputationalmethod

I “Exotic”optimizationconstraints

Yet it worked!

Results still validBecause of strong qualitative analysis

The past of computational homogeneous catalysis

Bottleneck:

Computer power

The present of computational homogeneous catalysis

What are

we doing?

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).

Similar, but not the same: two recent examples

I Larger and more complex systems:oxidative coupling

I Microkinetic models on reaction networks: host-guestcatalysis

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)

Computed cycle incompatible with experiment:Only CO2 extrusion should be observed!

Taking explicitly into account the copper species

Opening Pandora’s box

The key reductive elimination step

A schematic view of the same transition state

A mechanism different from conventional reductiveelimination

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?

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

Host-guest catalysis

nanoreactor, nanovessel, capsuleSpecial issue in Chem. Soc. Rev. in 2015

edited by Ballester, P.; Fujita, M.; Rebek, J. Jr.

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).

Initial calculation of catalytic cycle (kcal/mol)

Complex reaction network: need for a full microkineticmodel

Evolution of concentrations through time

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!

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?

This computed reaction network reproduces all availableexperimental data

The present of computational homogeneous catalysis

Bottleneck:

Human power

The future (?) of computational homogeneous catalysis

What do

we want to do?

Where do we want to go?

I More challenging experimental problems

I Big data treatment

I Descriptors for chemical reactivity

Challenging problems: water oxidation

I. Funes-Ardoiz, P. Garrido-Barros, A. Llobet, F. Maseras; in preparation

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/

Descriptors: statistical treatment of metal-ligand BDE

O. Lakuntza, M. Besora, F. Maseras; in preparation

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

Our computational group at ICIQ May ’16