Sponsored By

Sponsored by:

PRESENTATION

We welcome all participants to the “Computational Catalysis for Sustainable Chemistry” conference held at the Institute of Chemical Research of Catalonia (ICIQ) in Tarragona. The city was designated by UNESCO as a Humankind Heritage Site, which enjoys some of the best preserved Roman ruins in the Iberian Peninsula.

This event is a satellite of the “16th International Congress of Quantum Chemistry” (Menton, France) and takes place in the week preceding it.

The “Computational Catalysis for Sustainable Chemistry” symposium aims to bring chemists from around the world and is centered in the application of the most recent advances in computational chemistry to the field of catalysis. We strongly believe this meeting offers an excellent opportunity to meet prestigious speakers and exchange knowledge between the participating groups and strengthen the ties that may lead to future collaborations.

This will be also an occasion to remember Prof. Keiji Morokuma and celebrate his legacy. Prof. Morokuma was involved in the initial design of the conference and was scheduled to be its co-chairman. Unfortunately, he had health problems over the last year and passed away on November 27th, 2017 from heart failure.

We strongly encourage young scientists, particularly graduate students and postdoctoral fellows, to actively participate in the plenary lectures and a poster session.

We wish you all a wonderful time in Tarragona!

Feliu Maseras ICIQ Group Leader Chairperson – Computational Catalysis for Sustainable Chemistry

SPEAKERS

Ainara Nova – University of Oslo (Norway) Ataualpa A. C. Braga – Universidade de São Paulo (Brazil) Fahmi Himo – Stockholm University (Sweden) Franziska Schoenebeck – RWTH Aachen University (Germany) Jeremy Harvey – KU Leuven (Belgium) Joachim Sauer – Humboldt Universität zu Berlin (Germany) Kathrin Helen Hopmann – UiT The Arctic University of Norway (Norway) Lionel Perrin – Université de Lyon (France) Luigi Cavallo – King Abdullah University of Science and Technology (S. Arabia) Maria Besora – Institut Català d’Investigació Química (Spain) Maria Joao Ramos – Universidade do Porto (Portugal) Maytal Caspary Toroker – Technion, Israel Institute of Technology (Israel) Miho Hatanaka – Nara Institute of Science and Technology (Japan) Natalie Fey – University of Bristol (United Kingdom) Per-Ola Norrby – AstraZeneca Gothenburg (Sweden) Rob Paton – University of Oxford (United Kingdom) Rong-Zhen Liao – Huazhong University of Science and Technology (China) Satoshi Maeda – Hokkaido University (Japan) Steven E. Wheeler – University of Georgia (USA) Walter Thiel – Max-Planck-Institut für Kohlenforschung (Germany)

PROGRAMME

Wednesday, 13th June

11:50 – 14:15 Registration

14:15 – 14:30 Opening Ceremony

Wednesday afternoon session. Chairperson: Feliu Maseras

14:30 – 15:05 Walter Thiel Computational Studies of Transition Metal Catalysis and Biocatalysis

15:05 – 15:40 Satoshi Maeda Artificial Force Induced Reaction Method: Its Implementation and Development

15:40 – 16:15 Kathrin Hopmann Selectivity!

16:15 – 16:50 Luigi Cavallo Tuning Proximal and Remote Steric Effects in the Rationalization of Catalytic Behavior

16:50 – 17:15 Coffee Break

17:15 – 17:50 Philippe Sautet Crucial role of metastable structures of Pt clusters for light alkane activation

17:50 – 18:25 Maria Besora What are Bond Dissociation Energies made out of?

Thursday, 14th June

Thursday morning session. Chairperson: Karinne Miqueu

9:00 – 9:35 Joachim Sauer Computational Catalysis – Rigor and Relevance

9:35 – 10:10 Miho Hatanaka Application of Automated Reaction Path Search Method to a Systematic Search of Transition States: A Case Study on Asymmetric Catalytic Reaction

10:10 – 10:45 Lionel Perrin When Computational Chemistry Meets Experiments in Polymerization Catalysis

10:45 – 11:15 Coffee Break

11:15 – 11:50 Maria Joao Ramos Understanding enzymes. Can we accurately predict mechanisms of enzymatic reactions?

11:50 – 12:25 Rob Paton Theory-Led Design of Chiral Catalysts

12:25 – 13:00 Rong-Zhen Liao Challenges in Modeling Water Oxidation Reactions

13:00 – 14:30 Lunch

Thursday afternoon session. Chairperson: Antoni Frontera

14:30 – 15:05 Fahmi Himo Quantum Chemical Modeling of Reactions in Confined Spaces

15:05 – 15:40 Maytal Toroker Proton transfer through the bulk and near surface catalysis in nickel oxides

15:40 – 16:15 Ataualpa Braga Computational studies on ligand-free Heck reactions

16:15 – 16:50 ioChem-BD team The ioChem-BD platform: a Big Data solution for computational chemistry

16:50 – 19:00 Poster Session

21:00 Symposium Dinner 5

Friday, 5th June

Friday morning session. Chairperson: Agustí Lledós

9:00 – 9:35 Franziska Schoenebeck Selective Catalysis – Insight and Application

9:35 – 10:10 Steven Wheeler Automated Computational Workflows for Asymmetric Catalyst Design

10:10 – 10:45 Natalie Fey Data-Driven Catalyst Discovery and Optimisation

10:45 – 11:15 Coffee Break

11:15 – 11:50 Per-Ola Norrby Virtual Screening in Asymmetric Catalysis

11:50 – 12:25 Ainara Nova New Approaches to the Conversion of CO2 to Methanol and Polycarbamates

12:25 – 13:00 Jeremy Harvey Mechanism and Kinetics in Homogeneous Catalysis: A Computational Viewpoint

13:15 – 13:30 Closing Ceremony

CONFERENCE ABSTRACTS (CA)

Conference Abstract 1 Walter Thiel

Computational Studies of Transition Metal Catalysis and Biocatalysis

Walter Thiel Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, Mülheim, Germany

In catalysis research, theoretical calculations have become a companion to experimental work, since they can provide valuable and complementary mechanistic insight [1]. Transition metal catalysis and organocatalysis can be investigated by density functional theory (DFT), possibly followed by ab initio single-point calculations at the coupled cluster level, while combined quantum mechanical/molecular mechanical (QM/MM) approaches have emerged as the method of choice for treating biocatalysis by enzymes. The lecture will outline the theoretical background and the strategies of computational work on catalysis and will then describe selected applications from our own research. Possible topics include enantioinversion in gold catalysis [2], Rh-catalyzed trans-hydrogenation of alkynes [3,4], and enzymatic reactions catalyzed by cytochrome P450cam [5], cyclohexanone monooxygenase [6,7], and the putative Diels-Alderase SpnF [8]. The examples presented will illustrate the chemical insights and the improved mechanistic understanding of catalytic reactions that can be provided by QM and QM/MM calculations. References [1] W. Thiel, Angew. Chem. Int. Ed. 2014, 53, 8605-8613. [2] M. K. Ilg, L. M. Wolf, L. Mantilli, C. Farès, W. Thiel, A. Fürstner, Chem. Eur. J. 2015, 21, 12279-12284. [3] M. Leutzsch, L. M. Wolf, P. Gupta, S. M. Rummelt, R. Goddard, C. Farès, W. Thiel, A. Fürstner, Angew. Chem. Int. Ed. 2015, 54, 12431-12436. [4] A. Guthertz, M. Leutzsch, L. M. Wolf, P. Gupta, M. Fuchs, W. Thiel, C. Farès, A. Fürstner, J. Am. Chem. Soc. 2018, 140, 3156-3169. [5] S. Shaik, S. Cohen, Y. Wang, H. Chen, D. Kumar, W. Thiel, Chem. Rev. 2010, 110, 949- 1017. [6] I. Polyak, M. T. Reetz, W. Thiel, J. Am. Chem. Soc. 2012, 134, 2732-2741. [7] G. Bistoni, I. Polyak, M. Sparta, W. Thiel, F. Neese, submitted. [8] Y. Zheng, W. Thiel, J. Org. Chem. 2017, 82, 13563-13571.

Conference Abstract 2 Satoshi Maeda

Artificial Force Induced Reaction Method: Its Implementation and Development

Satoshi Meadaa,b* a, Hokkaido University, Sapporo, 060-0810, Japan, b, National Institute for Materials Science (NIMS), Tsukuba, 305-0044, Japan. * Presenting or corresponding author: [email protected]

Finding reaction pathways and their networks is a significant task in theoretical studies on reaction kinetics and mechanisms. We have developed an automated reaction path search method termed "artificial force induced reaction (AFIR)" [1]. It has been applied for elucidation of mechanisms of various organic reactions [2]. The AFIR methed has been implemented in the global reaction route mapping (GRRM) program, where the AFIR method implementated for molecular systems is available in GRRM17 [3]. Another topic is its further development for its application to various reaction emvironments, such as photoreaction [4], solid state phase transition [5], reactions in solution or enzyme [6], and surface reaction [7]. An approach to estimate a lifetime (durability) of given molecule by the AFIR method combined with a new kinetic approach [8] will also be discussed [9].

References 1. S. Maeda, K. Morokuma, J. Chem. Phys. 2010, 132, 241102 (4 pages); S. Maeda, K. Ohno, K. Morokuma, Phys. Chem. Chem. Phys. 2013, 15, 3683-3701; S. Maeda, Y. Harabuchi, M. Takagi, T. Taketsugu, K. Morokuma, Chem. Rec. 2016, 16, 2232-2248. 2. For example, see: W. M. Sameera, S. Maeda, K. Morokuma, Acc. Chem. Res. 2016, 49, 763- 773; T. Yoshimura, S. Maeda, T. Taketsugu, M. Sawamura, K. Morokuma, S. Mori, Chem. Sci. 2017, 8, 4475-4488. 3. S. Maeda, Y. Harabuchi, M. Takagi, K. Saita, K. Suzuki, T. Ichino, Y. Sumiya, K. Sugiyama, Y. Ono, J. Comput. Chem. 2018, 39, 233-251. 4. Y. Harabuchi, T. Taketsugu, S. Maeda, Phys. Chem. Chem. Phys. 2015, 17, 22561-22565. 5. M. Takagi, T. Taketsugu, H. Kino, Y. Tateyama, K. Terakura, S. Maeda, Phys. Rev. B 2017, 95, 184110 (11 pages). 6. K. Suzuki, K. Morokuma, S. Maeda, J. Comput. Chem. 2017, 38, 2213-2221. 7. S. Maeda, K. Sugiyama, Y. Sumiya, M. Takagi, K. Saita, Chem. Lett. 2018, 47, 396-399. 8. Y. Sumiya, Y. Nagahata, T. Komatsuzaki, T. Taketsugu, S. Maeda, J. Phys. Chem. A 2015, 119, 11641-11649. 9. Y. Sumiya, S. Maeda, Chem. Eur. J. 2018, in press.

Conference Abstract 3 Kathrin H. Hopmann

Selectivity!

Kathrin H. Hopmann Hylleraas Centre for Quantum Molecular Sciences, Dept. of Chemistry, UiT- The Arctic University of Norway, N-9037 Tromsø, Norway *[email protected]

Insights into the mechanistic aspects of chemical reactions increasingly rely on the use of computational methods. Reaction mechanisms of relatively large systems can nowadays be modelled with reasonable speed and good accura-cies.1 The high accuracy has made it possible to reliably model properties that are dependent on small energy differences, such as enantioselectivities.1,2 However, mechanistic computations are often based on model substrates and do not attempt to reproduce experimental properties that could support the validity of the proposed reaction pathways. Here I will present mechanistic insights into transition metal-catalyzed hydrogenation reactions, and in particular, I will show how computation of the chemo- and enantioselectivities of real substrates can be used to evaluate the validity of proposed mechanisms.3,4

Fig.1 Left: A chiral acid affects the enantioselectivity of Fe-catalyzed hydrogenation through non-covalent interactions. Right: Computational mechanisms require verification to ensure the validity.

References 1. a) K. H. Hopmann, How accurate is DFT for iridium-mediated chemistry, Organometallics 2016, 35, 3795, b) K.H. Hopmann, Quantum chemical studies of asymmetric reactions: Historical aspects and recent examples, Int. J. Quantum Chem. 2015, 115, 1232. 2. K. H. Hopmann, Iron-Brønsted-acid-catalysed asymmetric hydrogenation: Mechanism and selectivity- determining interactions, Chem. Eur. J. 2015, 21, 10020. 3. G. R. Morello, H. Zhong, P. J. Chirik, K. H. Hopmann, Cobalt-catalysed alkene hydrogenation: A metallacycle can explain the hydroxyl activating effect and the diastereoselectivity, Chem. Sci. 2018, In Press. 4. G. R. Morello, K. H. Hopmann, A dihydride mechanism can explain the intriguing substrate selectivity of iron- PNP-mediated hydrogenation, ACS Catal. 2017, 7, 5847.

Conference Abstract 4 Luigi Cavallo

Tuning Proximal and Remote Steric Effects in the Rationalization of Catalytic Behavior

Luigi Cavallo KAUST Catalysis Center, King Abdullah University of Science and Technology, Thuwal 23955-6900, Saudi Arabia Email: [email protected]

Rationalizing the behavior of transition metal catalysts often consists in relating their performance to the steric and electronic properties of the ligand. As for steric effects, the classical Tolman cone angle θ developed for phosphane type ligands certainly is among the most famous.1 However, this descriptor is biased towards phosphanes, which makes it less useful when different type of ligands have to be analyzed. In this scenario we developed 2,3 another descriptor, the percent of buried volume %VBur, which has been used to correlate catalytic behavior to the structure of the catalyst using typical structure-property relationships.4 As typical for numerical descriptors, the %VBur only captures average properties of a given ligand, missing completely the way space occupation around the metal center occurs. To overcome this limitation we introduced topographic steric maps, as a natural evolution of the 3,5 %VBur. Steric maps allow having a clear image of the surface of interaction between the transition metal based catalyst and the substrate. Nonetheless, extracting numbers from steric maps to be used in multivariate linear correlations aimed at rationalizing experimental behavior is not straightforward. To this end, we developed a buried volume approach aimed at separating the coordination space around the metal into proximal and remote zones. In this contribution we will show how tuning the separation between proximal and remote zones, and how this separation allows to achieve good rationalization of catalytic behavior in a series of test cases.

References 1. C. A. Tolman Chem. Rev. 1977, 77, 313-348. 2. A. Poater, B. Cosenza, A. Correa, S. Giudice, F. Ragone, V. Scarano, L. Cavallo Eur. J. Inorg. Chem. 2009, 1759-1766. 3. L. Falivene, R. Credendino, A. Poater, A. Petta, L. Serra, R. Oliva, V. Scarano, L. Cavallo Organometallics 2016, 35, 2286-92. 4. L. Falivene, L. Cavallo, G. Talarico ACS Catal. 2015, 5, 6815-21. 5. F. Ragone, A. Poater, L. Cavallo J. Am. Chem. Soc. 2010, 132, 4249-4258.

Conference Abstract 5 Philippe Sautet

Crucial role of metastable structures of Pt clusters for light alkane activation

Geng Sun and Philippe Sautet* Department of Chemical and Biomolecular engineering, Department of Chemistry and Biochemistry, University of California Los Angeles, Los Angeles, CA 90095, United States * Presenting: [email protected]

The determination of the structure of heterogeneous catalytic systems, under reaction conditions, is a key point for a detailed understanding of the nature of active sites and for the rational design of efficient catalysts. The lecture will focus on the modelling of small Pt cluster (Pt13) under hydrogen pressure and on their reactivity for methane and ethane activation.1 The approach combines Density Functional Theory, high-dimensional Neural Networks and evolutionary techniques. The bare Pt clusters shows a large number of low energy isomers (> 60 in 0.5 eV). Hydrogenated clusters adopt different geometries and appear more rigid, with a smaller number of low energy isomers. These metastable isomers nevertheless play a major role for the catalytic reactivity of the hydrogen covered cluster, which cannot be described by considering the most stable structure alone. Fluxionality and accessible metastable structure are hence key characteristics for the catalytic properties of small Pt clusters.

Reference 1. G. Sun, P. Sautet, Metastable Structures in Cluster Catalysis from First-Principles: Structural Ensemble in Reaction Conditions and Metastability Triggered Reactivity, J. Am. Chem. Soc. 2018, 140, 2812−2820.

Conference Abstract 6 Maria Besora

What are Bond Dissociation Energies made out of?

Maria Besora,a,* a, Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Tarragona, Catalonia *[email protected]

Statistical analysis is a powerful tool to extract meaningful information from large sets of data. Its techniques have been applied with success to large sets of data from very different areas of knowledge, also in computational chemistry.1-3 We have used them to study what the metal-ligand bond is made out of. We computed by DFT means the bond dissociation energies (BDE) between a wide variety of metal fragments and ligands. Statistical analysis reveals that a simple mathematical formula is able to estimate BDEs within a few kcal/mol from the DFT value. An extension of this treatment to a new set of metal fragments and ligands has been proven to reproduce with high accuracy the BDEs for this new set of data. With the aim of extracting chemical conclusions from the mathematics we have analyzed the mathematical expression obtained. Thanks to this analysis we can point to the fundamental aspects of metal-ligand bonding and give a hint of their relevance (Scheme 1).

Scheme 1

References 1. A. G. Maldonado, G. Rothenberg, Chem. Soc. Rev. 2010, 39 , 1891–1902. 2. N. Fey, Chem. Cent. J. 2015, 9, 38. 3. C. B. Santiago,J. Y. Guo, M. S. Sigman, Chem. Sci. 2018, 9, 2398-2412.

Conference Abstract 7 Lionel Perrin

Conference Abstract 8 Joachim Sauer

Computational Catalysis – Rigor and Relevance Joachim Sauer Institut für Chemie, Humboldt-Universität zu Berlin, Unter den Linden 6, 10099 Berlin, Germany

Quantum chemistry can remove the ambiguity connected with parameter fitting in microkinetic models, but only when rate and equilibrium constants for crucial steps can be predicted with chemical accuracy (4 kJ/mol for energies and one order of magnitude for rate constants). This has recently been achieved for the methylation of ethene, propene and butene in H-ZSM-5. Following a divide-and-conquer strategy, the common energy calculations on periodic models based on density functional theory are augmented with the more accurate wave-function type calculations for cluster models of the reaction site (Møller-Plesset perturbation theory (MP2) and Coupled Cluster theory (CCSD(T)). The availability of rigorous methods for calculating kinetic parameters of crucial reaction steps proved very useful when re-considering the well-established “Lunsford” mechanism for the oxidative coupling of methane on Li-doped MgO, which proposes that the C–H bond is activated by homolytic splitting involving hydrogen atom transfer to the O•– sites. For the oxygen radical sites of Li-doped MgO, our calculations yielded barriers for hydrogen abstraction between 7 and 27 (±6) kJ/mol, which were in obvious conflict with the much larger observed values, between 85 and 160 kJ/mol. Microkinetic simulations yielded 139 kJ/mol. From this disagreement we concluded that the Li+O•– site may not be the active site, and that methyl radicals released into the gas phase are not formed by hydrogen transfer to such sites. These findings stimulated further calculations. They have shown that the

Lunsford mechanism needs to be revised and that CH4 chemisorbs heterolytically on morphological defects. 2+ 2– + – [Mg O ]MgO + H–CH3 → [(Mg–CH3) HO ]MgO

Release of methane into the gas phase happens only when O2 is present on the surface, + – •– 2+ – • [(Mg–CH3) HO ]MgO + O2 → (O2 )[Mg HO ]MgO + CH3 Our quantum calculations, in combination with experiments, suggest a new role of the oxide catalyst in the oxidative coupling reaction. They do not provide and receive back electrons as transition metal oxide catalysts do in selective oxidations (Mars-van Krevelen mechanism), they rather stay inert with their own electronic system and just bring together the reactants allowing them to exchange electrons (redox equivalents) directly between themselves.

Conference Abstract 9 Miho Hatanaka

Application of Automated Reaction Path Search Method to a Systematic Search of Transition States: A Case Study on Asymmetric Catalytic Reaction

Miho Hatanakaa,b* a, Institute for Research Initiatives, Division for Research Strategy, Graduate School of Science and Technology, Data Science Center, Nara Institute of Science and Technology, Ikoma, Nara, Japan. b, JST PRESTO, Honcho, Saitama, Japan * [email protected]

Highly stereoselective reactions have been achieved by using chiral catalysts, and the computational chemistry contributed to better understanding of the mechanism of such reactions. Conventional chiral catalysts usually have rigid structures and bulky side chains on chiral centers to restrict the approach directions of reactants. Recently, a number of catalytic systems having flexible structures have been Figure 1. Schimatic picture of reported. There could be a large number of TSs that the AFIR method may contribute to the stereoselectivity, and a few selective TSs may not be enough. To overcome this No Barrier E (r ) + a r problem, an automated exploration method called the AB AB artificial force induced reaction (AFIR) method is one Artificial force E (r ) of the most suitable strategies. [1-2] AB a rAB We focused on the copper catalyzed TS A + B enantioselective proton migration from skipped enynes to chiral allenes. [3] The regioselectivity of AB this reaction depended on the chiral ligands. To understand the mechanism, we explored the TSs of the region-determining step by using the AFIR method and found that the steric hindarance around the copper controlled the energy difference between the TSs forming the major and minor products. In this talk, the strategy to design the appropliate ligand will be also discussed.

References 1. S. Maeda, K. Ohno, K. Morokuma. Phys. Chem. Chem. Phys. 2013, 15, 3683-3701. 2. S. Maeda, Y. Harabuchi, M. Takagi, T. Taketsugu, K. Morokuma, Chem. Rec. 2016, 16, 2232-2248. 3. X.-F. Wei, M. Hatanaka, T. Itoh, H.L. Li, Y. Shimizu, M. Kanai, submitted.

Conference Abstract 10 Raghavan B. Sunoj

Transition State Models toward Understanding Chiral Induction in Asymmetric Dual Catalysis

Raghavan B. Sunoj

Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076 India

Computational quantum chemistry has been increasingly employed toward rationalizing the stereochemical outcome in catalytic reactions.1 The approach typically involves the identification of kinetically significant transition states and intermediates. In our laboratory, ab initio as well as DFT methods are employed to gain insights into carbon-carbon and carbon-heteroatom bond-forming reactions of immediate practical significance.2 The key objective of our research is to gain molecular insights on the factors responsible for stereoselectivity and to exploit such insights toward in silico design of novel asymmetric catalysts.3 A number of examples wherein the conventional transition state models required systematic refinements toward accounting the observed product distribution and stereochemical outcome will be presented. Through this talk, we intend to propose the need for a timely rethink on a number of working hypotheses on asymmetric induction that places an over-emphasis on steric interaction. In general, the presentation would encompass a few contemporary themes in the domain of asymmetric multi-catalytic reactions.4 Interesting interpretations/rationalizations of experimental observations besides meaningful guidelines for rational improvements in the design of asymmetric catalysts would remain the key focus of the presentation. The contents are designed to cater to a broad and diverse group of audience; hence, the chemical insights would be emphasized, rather than a labyrinth of technical details.

[1] (a) P. H. –Y. Cheong, C. Y. Legault, J. M. Um, N. Celebi-Olcum, K. N. Houk, Chem. Rev. 111, 5042 (2011). (b) R. B. Sunoj, Wiley Interdisciplinary Reviews: Comput. Mol. Sci. 1, 920 (2011). [2] (a) G. Jindal, R. B. Sunoj, Angew. Chem., Int. Ed. 53, 4432 (2014). (b) R. B. Sunoj, Acc. Chem. Res. 49, 1019 (2016). [3] (a) C. B. Shinisha, R. B. Sunoj, Org. Biomol. Chem. 5, 1287 (2007). (b) G. Jindal, Sunoj, R. B. Org. Bimol. Chem. 12, 2745 (2014). [4] (a) G. Jindal, R. B. Sunoj, J. Am. Chem. Soc. 136, 15998 (2014). (b) G. Jindal, H. K. Kisan, R. B. Sunoj, ACS Catal. 5, 480 (2015). (c) B. Bhaskararao, R. B. Sunoj, J. Am. Chem. Soc. 137, 15712 (2015). (d) B. Bhaskararao, R. B. Sunoj, ACS Catal. 7, 6675 (2017).

Conference Abstract 11 Maria Joao Ramos

Understanding enzymes Can we accurately predict mechanisms of enzymatic reactions?

Maria João Ramos UCIBIO@REQUIMTE, Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre s/n, 4169-007 Porto, Portugal

* [email protected]

We know that we can establish catalytic mechanisms of enzymatic reactions and, in doing so, explain the findings of experimentalists, but can we actually predict them? This talk is concerned with the computational needs that we come across to figure out results within computational enzymology. Calculations devised to study protein interactions and circumvent problems in some relevant systems will be reported as well as recent developments in the establishment of some catalytic mechanisms. We have resorted to QM/MM (1,2) as well as other calculations (3,4), in order to analyse the energetics of processes related to the systems under study and evaluate their feasibility according to the available experimental data.

References 1. Cerqueira, Gonzalez, Fernandes, Moura, Ramos, Acc. Chem. Res., 48, 2875, 2015 2. Neves, Fernandes, Ramos, PNAS, 114, E4724, 2017 3. Oliveira, Cerqueira, Fernandes, Ramos, JACS 133, 15496, 2011 4. Gesto, Cerqueira, Fernandes, Ramos, JACS 135, 7146, 2013

Conference Abstract 12 Rob Paton

Theory-Led Design of Chiral Catalysts

Robert S. Patona* a Dept. of Chemistry, Colorado State University, Fort Collins, CO 80523, USA * [email protected]

"Prediction is difficult, especially about the future." This phrase, whether first uttered by a baseball catcher, quantum physicist or great American novelist,1 pithily sums up the challenge of computational catalyst design. In this talk I discuss some inherent challenges involved in the quantitative prediction of catalytic selectivity and our approaches to overcome them.2 The development of bespoke transition state force fields and classical molecular dynamics simulations are particularly well-suited to the study of conformationally flexible systems used experimentally.3 These methods underpin quantum-chemical studies and, alongside experiment collaborators, have been used to develop new highly-enantioselective homogeneous catalysts.4,5

References 1. Yogi Berra, Neils Bohr and Mark Twain have all been credited with these famous words (http://larry.denenberg.com/predictions.html) 2. Q. Peng, F. Duarte, R. S. Paton, Chem. Soc. Rev. 2016, 45, 6093–6107. 3. (a) C. P. Johnston, A. Kothari, T. Sergeieva, S. I. Okovytyy, K. E. Jackson, R. S. Paton, M. D.; Smith, M. D. Nature Chem. 2015, 7, 171–178; (b) A. Madarász, D. Berta, R. S. Paton J. Chem. Theor. Comput. 2016, 12, 1833–1844. 4. R. Straker, Q. Peng, A. Mekareeya, R. S. Paton, E. A. Anderson, Nature Commun. 2016, 7, 10109. 5. G. Pupo, F. Ibba, D. M. H. Ascough, A. C. Vicini, P. Ricci, K. Christensen, J. R. Morphy, J. M. Brown, R. S. Paton, V. Gouverneur, Science 2018, 360, 638–642.

Conference Abstract 13 Rong-Zhen Liao

Challenges in Modeling Water Oxidation Reactions

Rong-Zhen Liao

Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology,Wuhan 430074, P. R. China [email protected]

Water splitting driven by light is a promising technology for supplying clean and sustainable fuel by production of hydrogen. The oxidation of water by releasing four protons and four electrons is thermodynamically unfavorable with a relatively large energy demand

(E0=1.23 V vs SHE at pH=0), and is therefore quite challenging to accomplish. During the last few decades, considerable progress has been achieved in the development of homogeneous water oxidation catalysts (WOCs) using transition metals.[1] Quantum chemical calculations[2] have been used to elucidate the mechanism of water oxidation promoted by a number of catalysts incorporating Ru,[3] Ir,[4] Fe,[5] Mn,[6] and Cu.[7] In this talk, some of the challenges in the modeling are discussed.

References: [1] Kärkäs, M. D.; Verho, O.; Johnston, E. V.; Åkermark, B. Chem. Rev. 2014, 114, 11863-12001. [2] Liao, R.-Z.; Siegbahn, P. E. M. ChemSusChem 2017, DOI: 10.1002/cssc.201701374. [3] (a) Laine, T. M.; Kärkäs, M. D.; Liao, R. Z.; Åkermark, T.; Lee, B.-L.; Karlsson, E. A.; Siegbahn, P. E. M.; Åkermark, B. Chem. Comm. 2015, 51, 1862-1865. (b) Laine, T. M.; Kärkäs, M. D.; Liao, R. Z.; Siegbahn, P. E. M.; Åkermark, B. Chem. Eur. J. 2015, 21, 10039-10048. (c) Kärkäs, M. D.; Liao, R. Z.; Laine, T. M.; Åkermark, T.; Karim, S. R.; Siegbahn, P. E. M.; Åkermark, B. Catal. Sci. Technol. 2016, 6, 1306-1319. (d) Liao, R. Z.; Kärkäs, M. D.; Laine, T. M.; Åkermark, B.; Siegbahn, P. E. M. Catal. Sci. Technol. 2016, 6, 5031–5041. (e) 62.Abdel-Magied, A. F.; Shatskiy, A.; Liao, R.-Z.; Laine, T. M.; Arafa, W. A. A.; Siegbahn, P. E. M.; Karkas, M. D.; Akermark, B.; Johnston, E. V. ChemSusChem 2016, 9, 3448-3456. [4] Liao, R. Z.; Siegbahn, P. E. M. ACS Catal. 2014, 4, 3937-3949. [5] Liao, R. Z.; Li, X.-C.; Siegbahn, P. E. M. Eur. J. Inorg. Chem. 2014, 728-741. [6] (a) Liao, R. Z.; Siegbahn, P. E. M. J. Photochem. Photobiol. B 2015, 152,162- 172. (b) Liao, R. Z.; Kärkäs, M. D.; Lee, B.-L.; Åkermark, B.; Siegbahn, P. E. M. Inorg. Chem. 2015, 54, 342-351. (c) Li, Y.-Y.; Siegbahn, P. E. M.; Liao, R. Z. ChemSusChem 2017, 10, 903-911. (d) Liao, R.-Z.; Siegbahn, P. E. M. J. Catal. 2017, i354, 169-181. [7] Su X.-J.; Gao, M.; Jiao, L.; Liao, R.-Z.; Siegbahn, P. E. M.; Cheng, J.-P.; Zhang, M.-T. Angew. Chem. Int. Ed. 2015, 54, 4909-4914. 20

Conference Abstract 14 Fahmi Himo

Quantum Chemical Modeling of Reactions in Confined Spaces

Fahmi Himo Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-10691 Stockholm, Sweden. [email protected]

This talk will discuss our recent efforts in using DFT calculations to study reactions inside synthetic self-assmebled capsules. A number of examples will be described, including the cycloaddition between azide and acetylene, and the reaction between carboxylic acids and isonitriles. Description of these reactions requires: 1) structural and energetic characterization of the capsules, 2) accurate determination of the binding free energies of all possible guests, including reactants, solvent and solvent impurities, and 3) calculation of the reaction pathways inside and outside the capsule. We show that the dispersion-corrected B3LYP method with the quasi-RRHO correction provides a reasonable approach for this purpose. Detailed energy decomposition analysis is applied to identify the factors causing the rate enhancement and the selectivity introduced by the capsule.

Conference Abstract 15 Maytal Caspary Toroker

Proton transfer through the bulk and near surface catalysis in nickel oxides

Maytal Caspary Toroker

Department of Materials Science and Engineering, Technion - Israel Institute of Technology, Haifa 3200003, Israel

Abstract

Metal oxides are often used as catalysts for the oxygen evolution reaction which is of significant importance for water splitting as an alternative energy source energy. However, metal oxides may allow diffusion of hydrogen atoms whose positions are not fully determined experimentally. In order to understand how hydrogen diffusion affects catalytic efficiency, we use Density Functional Theory+U (DFT+U) calculations that model oxygen evolution reaction catalysis for pure and doped metal oxide materials. Our calculations reveal that hydrogen diffusion is possible in some doped cases. This could provide insights on the duality of proton and charge transfer at the surface of reactive materials.

References: 1. V. Fidelsky and M. Caspary Toroker, “Enhanced water oxidation catalysis of nickel oxyhydroxide through the addition of vacancies”, J. Phys. Chem. C 120, 25405 (2016). 2. V. Butera and M. Caspary Toroker, “Electronic properties of pure and Fe-doped beta- Ni(OH)2: New insights using density functional theory with a cluster approach”, J. Phys. Chem. C 120, 12344 (2016). 3. V. Fidelsky, V. Butera, J. Zaffran, M. Caspary Toroker, “Three fundamental questions on one of our best water oxidation catalysts: a critical perspective”, Theor. Chem. Acc., 135:162 (2016). 4. V. Fidelsky, D. Furman, Y. Khodorkovsky, Y. Elbaz, Y. Zeiri, and M. Caspary Toroker, “Electronic structure of beta-NiOOH with hydrogen vacancies and implications for energy conversion applications”, invited paper to MRS Communications, DOI: https://doi.org/10.1557/mrc.2017.26, 1-8 (2017). 5. Y. Elbaz and M. Caspary Toroker, “Dual mechanisms: Hydrogen transfer during water oxidation catalysis of pure and Fe-doped nickel oxyhydroxide”, J. Phys. Chem. C 121, 16819 (2017).

Conference Abstract 16 Ataualpa A.C. Braga

Computational studies on ligand-free Heck reactions

Vitor H. Menezes da Silvaa,b, Bruno M. Servilhaa, Carlos R. D. Correiab, Ataualpa A. C. Bragaa*

a, Dep. de Química Fundamental, IQ-USP, São Paulo-SP, Brazil. b Dep. de Química Orgânica, IQ-Unicamp, Campinas-SP, Brazil *E-mail: [email protected]

In this talk, it will be discussed the last results obtained by our group involving the theoretical study on the full catalytic cycle of ligand-free Heck cross-coupling reaction (i.e. Heck- Matsuda reactions) involving a variety of substrates (nucleophiles) with arenediazonium salt as electrophile. Our results also show the non-covalent directing efects in both, Heck- Matsuda and oxidative Heck reactions, allowing the preferential formation of cis-substituted aryl cyclopentenes containing two stereocenters, including quaternary stereocenters. The mechanism and origin of stereoselectivity were investigated with control experiments and DFT calculations which fully support the stabilizing internal out-of-coordination-sphere ion- dipole interaction between the resident functional group and the cationic palladium. 1,2

References 1. J. O. Silva, R. A. Angnes, V. H. M. Silva, B. M. Servilha, M. Adeel, A. A. C. Braga, A. Aponick, C. R. D. Correia, J. Org.Chem. 2016, 81, 2010–2018; 2. J. M. Oliveira, R. A. Angnes, I. U. Khan, E. C. Polo, G. Heerdt, B. M. Servilha, V. H. Menezes da Silva, A. A. C. Braga, C. R. D. Correia; Chem. Eur. J. 2018. Accepted, doi:10.1002/chem.201801910.

Conference Abstract 17 Franziska Schoenebeck

Selective Catalysis – Insight and Application Franziska Schoenebeck RWTH Aachen University, Institute of Organic Chemistry, Landoltweg 1, 52074 Aachen, Germany e-mail: [email protected]

Detailed understanding of catalytic transformations is key to designing better catalysts. This talk will give insights on case studies and reactivity designs recently undertaken in our laboratory in the area of homogeneous Pd- and Ni-catalysis for the introduction of fluorinated groups into organic molecules and to tackle chemoselectivity challenges in C-C bond formations.[1] A combination of experimental and computational tools were applied in these studies.[2] The lecture will showcase diverse applications of computational chemistry in organic chemistry, ranging from (i) gaining mechanistic understanding post experiment, (ii) the prediction and design of a ligand/catalyst prior to experiment, and (iii) a rational reaction development (prediction of scope) in concert with experiment.

References

[1] Representative examples: a) Kalvet, I.; Magnin, G.; Schoenebeck, F. Angew. Chem. Int. Ed. 2017, 56,1581; b) Yin, G.; Kalvet, I.; Schoenebeck, F. Angew. Chem. Int. Ed. 2015, 54, 6809; c) Dürr, A. B.; Yin, G.; Kalvet, I.; Napoly, F.; Schoenebeck, F. Chem. Sci. 2016, 7, 1076; d) Nielsen, M. C.; Bonney, K. J.; Schoenebeck, F. Angew. Chem. Int. Ed. 2014, 53, 5903. [2] For recent reviews on the combination of computation and experiment, see: a) Sperger, T.; Sanhueza, I. A.; Schoenebeck, F. Acc. Chem. Res. 2016, 49, 1311; b) Sperger, T.; Sanhueza, I. A.; Kalvet, I.; Schoenebeck, F. Chem. Rev. 2015, 115, 9532; c) Bonney, K. J.; Schoenebeck, F. Chem. Soc. Rev. 2014, 43, 6609.

Conference Abstract 18 Steven Wheeler

Automated Computational Workflows for Asymmetric Catalyst Design

Yanfei Guana, Steven E. Wheelerb* a, Department of Chemistry, Texas A&M University, College Station, TX (USA). b, Center for Computational Quantum Chemistry, Department of Chemistry, University of Georgia, Athens, GA (USA). * Presenting or corresponding author: [email protected]

Despite the widespread success of modern quantum chemistry in explaining the origin of activity and selectivity in asymmetric catalysis, the computational design of new catalyst is still far from routine [1]. Ideally, one could identify new catalysts by screening virtual libraries of potential designs. In this way, only those designs predicted to be most highly active and selective would need to be synthesized and tested experimentally. We will discuss the many technical and conceptual challenges that have hampered such efforts to use quantum chemistry for catalyst design. Then we will discuss our computational toolkit AARON (An Automated Reaction Optimizer for New catalysts) and the underlying tools (AaronTools), which automates the 100s of transition state structure optimizations that need to be executed in order to provide robust predictions of the stereoselectivity and activity of realistic asymmetric catalysts [2]. Applications of AARON will be discussed in the context of asymmetric organocatalysis [3] and metal-based catalysis [4].

References 1. K. N. Houk, F. Liu, Acc. Chem. Res. 2017, 50, 539-543. 2. Y. Guan, V. M. Ingman, B. J. Rooks, S. E. Wheeler (in preparation). 3. A. C. Doney, B. J. Rooks, T. Lu, S. E. Wheeler, ACS Catal. 2016, 6, 7948-7955. 4. Y. Guan, S. E. Wheeler, . Angew. Chem. Int. Ed., 2017, 56, 9101-9105.

Conference Abstract 19 Natalie Fey

Data-Driven Catalyst Discovery and Optimisation

Natalie Feya* a, School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS . * [email protected]

Computational studies of organometallic homogeneous catalysis play an increasingly important role in furthering (and changing) our understanding of catalytic cycles and can help to guide the discovery and evaluation of new catalysts.1 While a truly “rational design” process remains out of reach, detailed mechanistic information can be combined successfully with parameters characterising catalysts to predict outcomes and guide screening.2 This process relies on large databases of parameters characterising ligand3 and complex properties.4 Combining these with figures-of-merit for catalyst performance can lead to powerful predictive models. However, catalysis is not (statistically) normal and I will draw on recent work to illustrate some of the challenges in the journey towards large-scale computational prediction.

References 1. a) C. L. McMullin, N. Fey, J. N. Harvey, Dalton Trans., 2014, 43, 13545 – 13556. b) N. Fey, M. Garland, J. P. Hopewell, C. L. McMullin, S. Mastroianni, A. G. Orpen, P. G. Pringle, Angew. Chem. Int. Ed. 2012, 51, 118-122. 2. J. Jover, N. Fey, Chem. Asian J., 2014, 9, 1714-1723. 3. J. Jover, N. Fey, J. N. Harvey, G. C. Lloyd-Jones, A. G. Orpen, G. J. J. Owen-Smith, P. Murray, D. R. J. Hose, R. Osborne, M. Purdie, Organometallics, 2012, 31, 5302-5306. 4. O. J. S. Pickup, I. Khazal, E. J. Smith, A. C. Whitwood, J. M. Lynam, K. Bolaky, T. C. King, B. W. Rawe, N. Fey, Organometallics, 2014, 33, 1751-1791.

Conference Abstract 20 Per-Ola Norrby

Virtual Screening in Asymmetric Catalysis

Per-Ola Norrby* Early Product Development, Pharmaceutical Sciences, IMED Biotech Unit, AstraZeneca Gothenburg, Pepparedsleden 1, SE-431 83 Mölndal, Sweden *[email protected]

Abstract text: Finding a suitable catalyst for a desired asymmetric transformation is a major challenge in the pharmaceutical industry. In AstraZeneca, we want to simplify this problem by using computational methods that are fast and accurate enough to allow a virtual screening of potential catalytic systems. We have implemented a workflow, called CatVS, that allows a user to draw the structure in a simple web-based interface and submit it to a predefined workflow. A ligand library is screened for selectivity, and a list containing highly selective catalysts is emailed back to the user within a day, Figure 1. In this talk, I will outline the machinery we use for this workflow, based on our previously published Q2MM method.1 I will also show our initial attempts to apply this method for predictive catalyst selection in an industrial setting.2

Figure 1 CatVS workflow

References 1. E. Hansen, A. Rosales, B. Tutkowski, P.-O.Norrby, O. Wiest, Acc. Chem. Res. 2016, 49, 996-1005. 2. A.R. Rosales, J. Wahlers, E. Limé, R.E. Meadows, K.W. Leslie, R. Savin, F. Bell, E.C. Hansen, P. Helquist, R.H. Munday, O. Wiest, P.-O. Norrby, submitted

Conference Abstract 21 Ainara Nova

New Approaches to the Conversion of CO2 to Methanol and Polycarbamates

Ainara Nova* Hylleraas Centre for Quantum Molecular Sciences, Department of Chemistry, University of Oslo, Sem Sælandsvei 26, Oslo, Norway. * [email protected]

Using CO2 as a building block in organic synthesis will contribute to the development of a renewable carbon economy and is potentially a sustainable strategy for CO2 capture and storage (CCS). In particular, the hydrogenation of CO2 to methanol may provide the possibility of converting a harmful byproduct in a liquid fuel and versatile chemical feedstock. Ru bifunctional catalysts have already shown their potential to perform this reaction efficiently by using amines as co-catalyst.[1] This reaction involves several transformations (see Scheme), including the hydrogenolysis of amides as one of the most challenging. In order to improve the efficiency of this reaction with a cheaper and less toxic Fe catalyst (Cat),[2] the mechanistic details of this complex transformation are being investigated in our group by using DFT methods. In addition, the same methodology has been used to predict an unprecedented reaction that may allow for the conversion of CO2 to polycarbamates by reaction with imines. The feasibility of this reaction is based on previous work of our group[3] suggesting that imines should co-polymerize with CO2 as epoxides do to yield polycarbonates.

References 1. a) M. S. Sanford, et al. J. Am. Chem. Soc., 2015, 137, 1028. b) G. K. S. Prakash, et al. J. Am. Chem. Soc., 2016, 138, 778. 2. N. Hazari, W. Bernskoetter, et al. Organometallics 2017, 36, 409. 3. a) Nova, A.; Hazari, N. et al. Chem. Eur. J., 2012, 18, 6915. b) Crabtree, R. H.; Hazari, N.; Maseras, F.; Nova A. et al. Inorg. Chem., 2012, 51, 9683.

Conference Abstract 22 Jeremy Harvey

Mechanism and Kinetics in Homogeneous Catalysis: A Computational Viewpoint

Jeremy Harvey * KU Leuven, Department of Chemistry, Celestijnenlaan 200F, B-3001 Leuven, Belgium * [email protected]

Reaction mechanisms are often of great interest in catalysis, as they offer some of the insight needed in order to develop improved catalysts or conditions. Characterizing reaction kinetics – in terms both of individual rate constants and in terms of the overall time-dependence of concentrations – as well as the mechanism is even more valuable. Accordingly, computational chemistry has long sought to address reaction mechanisms. Qualitatively, ab initio or density functional theory (DFT) electronic structure methods are well known to be able to characterize mechanisms in a valuable way, e.g. by identifying the structure of elusive intermediates or of transition states. Quantitative predictions of mechanisms, in the sense of using computation to calculate reaction kinetics, is more elusive.

In this talk, I will discuss recent progress and challenges in this area emerging from both published [1,2,3] and unpublished work in my group concerning this problem.

References 1. Z. Liu, C. Patel, J. N. Harvey and R. B. Sunoj, “Mechanism and reactivity in the Morita– Baylis– Hillman reaction: the challenge of accurate computations”, Phys. Chem., Chem. Phys. 2017, 9, 30647. 2. S. Essafi, S. Tomasi, V. K. Aggarwal and J. N. Harvey, “Homologation of Boronic Esters with Organolithium Compounds: A Computational Assessment of Mechanism”, J. Org. Chem., 2014, 79, 12148. 3. L. E. Rush, P. G. Pringle and J. N. Harvey, “Computational Kinetics of Cobalt-Catalyzed Alkene Hydroformylation”, Angew. Chem., Int. Ed., 2014, 53, 8672. pp. 1-20.

Conference Abstract 23 ioChem-BD Team

The ioChem-BD platform: a Big Data solution for computational chemistry

ioChem-BD Team Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. dels Paı̈ sos Catalans 16, 43007 Tarragona, Catalonia, Spain

The use of automated processing tools and workflows, the need to feed machine learning algorithms, and the exponential increase of computing power are favouring the generation of large datasets in the field of theoretical chemistry and materials science. Managing such datasets is becoming a major challenge. The computational groups at ICIQ are currently developing ioChem-BD,1 a web-based platform (http://www.iochem-bd.org) that stores scientific data, which is flexible to adapt to future requirements by its modular design. Three main modules cover the whole data lifecycle: creation, processing, visualisation, publishing and sharing (see drawing). This presentation will outline the main features of this platform with some practical examples of application.

References 1. M. Álvarez-Moreno, C. de Graaf, N. Lopez, F. Maseras, J. M. Poblet, C. Bo J. Chem. Inf. Model. 2015, 55, 95–103.

POSTER ABSTRACTS (PA)

Poster Abstract 1 Agnieszka Drzewiecka-Matuszek

Characterisation of vanadium centres introduced into BETA zeolite – theoretical and experimental approach

Agnieszka Drzewiecka-Matuszek, Małgorzata Smoliło, Katarzyna Samson, Dorota Rutkowska- Żbik * 1Jerzy Haber Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Krakow, Poland * Contact e-mail(s): [email protected]

The production of lower alkenes is of increasing interest because of their importance in the chemical industry. Oxidative dehydrogenation (ODH) is an attractive catalytic reaction of formation of light alkenes from light alkanes: CnH2n+2 + 0.5 O2 → CnH2n + H2O The energy demand for this reaction is much lower than that for conventional catalytic cracking and even than that of dehydrogenation processes [1]. Vanadium-based systems are an important class of ODH catalysts. The aim of this work was to gain deep insight into the nature of the V species introduced into the Beta zeolite by two-step post-synthesis method [2] and characterize obtained samples both theoretically and experimentally. We studied the nature of the introduced vanadium. Its coordination, oxidation state, and the existence of proximal hydroxyl groups were assessed by the experimental approaches with an aid from computations. The chemical composition of the samples was confirmed with XRF, phase composition by XRD, BET provided surface area and porosity. Reducibility was measured with H2-TPR method, while NH3-TPD gave information on the type and strength of acid centers. The theoretical investigations were performed within Density Functional Theory (DFT), with Perdew-Burke-Ernzerhof (PBE) functional and the basis set of def2- TZVP type with Turbomole computer program. In the first instance, theoretical cluster models of the possible vanadium active centres were constructed (Rys. 1), based on the available literature data as to the geometry and environment of the V-sites in zeolites, in particular the theoretical studies regarding SOD and BETA zeolites [3].

Rys. 1. Optimized geometry of an exemplary cluster with V-site in Beta zeolite.

References 1. F. Cavani, N. Ballarini, A. Cericola, Catal. Today 127 (2007) 113. 2. S. Dzwigaj, M.J. Peltre, P. Massiani, A. Davidson, M. Che, Chem. Comm. (1998) 8 3. A. Wojtaszek, M. Ziolek, S. Dzwigaj, F. Tielens, Chem. Phys. Lett. 514 (2011) 70

Acknowledgements: This work was supported by the National Science Centre, Poland within project no 2016/23/B/ST4/02854. 32

Poster Abstract 2 Albert Solé-Daura

Mechanistic study on the protein hydrolysis promoted by Zr- substituted Polyoxometalates

Albert Solé-Dauraa*, David Robinsonb, Josep M. Pobleta, Jonathan D. Hirstb, Jorge J. Carbóa a, Universitat Rovira I Virgili, C/ Marcel·lí Domingo 1, Tarragona, Spain b, University of Nottingham, University Park, Nottingham, UK * [email protected]

The importance of the selective hydrolysis of peptide bonds in proteins arises from its potential application in proteomics but also in the treatment of some diseases related to pathogenic proteins, such as Alzheimer’s disease. Interestingly, Zr(IV)-substituted polyoxometalates (POMs) have shown the ability to hydrolyse proteins in a selective manner.[1] As a representative case, we had selected hen egg-white lysozyme (HEWL), which is cleaved at Trp28-Val29 and Asn44-Arg45; and identified two cationic patches on the protein surface that can be related to the observed selectivity by means of Molecular Dynamics (MD) simulations.[2] However, the molecular mechanism responsible for the hydrolysis still remained poorly understood. Thus, in a step forward, we have performed a detailed mechanistic study combining different computational techniques. Classical and ab initio MD simulations were used to study the coordination process accounting for the required protein distortion. Static DFT calculations served to characterise the whole reaction mechanism using the reactive dipeptide within a ‘cluster model’ approach. Finally, hybrid quantum-mechanics/molecular mechanics (QM/MM) calculations were carried out to analyse more deeply some of the crucial steps on the real system (Figure 1).

Figure 1

References 1. H. G. T. Ly, G. Absillis, R. Janssens, P. Proost, T. N. Parac-Vogt, Angew. Chem. Int. Ed. 2015, 54, 7391-7394. 2. A. Solé-Daura, V. Goovaerts, K. Stroobants, G. Absillis, P. Jiménez-Lozano, J. M. Poblet, J. D. Hirst, T. N. Parac-Vogt, J. J. Carbó, Chem. Eur. J. 2016, 22, 15280-15289.

Poster Abstract 3 Andrea Darù

Computational study of Nickel-catalysed Negishi Arylation of Propargylic bromides

Andrea Darù*, Jeremy Harvey KU Leuven, Celestijnenlaan 200F, Heverlee, Belgium * Presenting or corresponding author: [email protected]

The current scenario on transition-metal catalysed reactions shows Palladium as the most widely used element in organic synthesis[1]. However, in the last decades the first row transition metals are gaining more interest. In fact, the use of those elements for greener and more sustainable reaction conditions is the main goal of most of the modern catalytic reaction studies. In this study we gained a better understanding about the stereoselective Negishi arylation reaction of propargylic bromides catalysed by Ni(iPr-pybox) proposed by Fu and co workers[2]. This reaction has been extensively studied experimentally, indicating that a ligand-centered radical Ni(I) complex is one of the species involved in the process. By using DFT calculations we are getting insight into this challenging reaction.

References 1. ACS Catal., 2015, 5 (3), pp 1964–1971 2. J. Am. Chem. Soc. 2014, 136, 16588−16593

Poster Abstract 4 Antonio Frontera

Anion–π catalysis on fullerenes

Antonio Fronteraa * a, Departament de Química, Universitat de les Illes Balears, Crta de Valldemossa km 7.5, 07122 Palma de Mallorca (Baleares), SPAIN * [email protected]

Anion-π interactions on fullerenes are poorly explored because theoretical understanding and synthetic accessibility are more demanding. However, the localized π holes on its surface promise unique selectivities, particularly with regard to anion-π catalysis. To elaborate on this promise, tertiary amines are attached nearby to turn on anion-π interactions as soon as the negative charge is injected into the substrate. Critically dependent on the precision of this positioning, the resulting stabilization of anionic intermediates and transition states on fullerenes is shown to selectively accelerate disfavored enolate addition and exo Diels–Alder reactions.1 The observed selectivities are fully consistent with computational simulations, particularly with regard to the discrimination of differently planarized and charge-delocalized enolate tautomers by anion-π interactions. In the presence of chiral interfacers, anion-π catalysis on the π sphere occurs with high enantioselectivity.

References 1. J. López-Andarias, A. Frontera, S. Matile, J. Am. Chem. Soc. 2017, 139, 13296.

Poster Abstract 5 Carles Bo

New Tools Around ioChem-BD for Computational Catalysis

Ana Mateoa, Joan González-Fabraa, Enric Petrusa, Moisés Álvareza,b, Martin Gumbaua, Carles Boa,b * a, Institute of Chemical Research of Catalonia, ICIQ, Avda. Països Catalans, 16, Tarragona. b, Departament de Química Física I Inorgànica, Universitat Rovira i Virgili, Tarragona. * Presenting or corresponding author: [email protected]

ioChem-BD1 is aimed at parsing, managing storing, and publishing computational chemistry datasets. Also, it provides tools to alleviate users of tedious tasks. Among other features, the Create module facilitates the construction and visualization of Reaction Energy Profiles directly from raw data. On the other hand, Fireworks2, a workflows manager system, appears very convenient to integrate ioChem-BD with any HPC environment, so to submit, upload and store results just computed in an automated manner. The new Create REST API interface allows interacting with and operating ioChem-BD databases remotely. We present here an example of such integration that allows almost automated computation of an existing reaction energy profile.

1. Álvarez-Moreno, M.; de Graaf, C.; López, N.; Maseras, F.; Poblet, J. M.; C, Bo, J. Chem. Inf. Model. 2015, 55 (1), 95. 2. Jain, A., Ong, S. P., Chen, W., Medasani, B., Qu, X., Kocher, M., Brafman, M., Petretto, G., Rignanese, G.-M., Hautier, G., Gunter, D., and Persson, K. A. (2015) Concurrency Computat.: Pract. Exper. 2015, 27, 5037.

Poster Abstract 6 Chen-Hao Yeh

Subambient C-H Activation of Methane over IrO2 Nanoparticles as Probed by In Situ Spectroscopic and Theoretical Studies

Yu-Cheng Liu†, a, Chen-Hao Yeh†, b, Yen-Fan Loa, Shawn D. Lina* and Jyh-Chiang Jiangb* a Catalysis Laboratory, b Computational and Theoretical Chemistry Laboratory, Department of Chemical Engineering, National Taiwan University of Science and Technology, No.43, Keelung Rd., Sec.4, Da'an Dist., Taipei 10607, Taiwan † These authors contributed equally to this work e-mail: [email protected]

ABSTRACT Development of an efficient process for CH4 utilization relies on new catalytic materials that show good activity under mild conditions. In this study, we demonstrate that IrO2 nanoparticles under atmospheric pressure activate the C-H bond and convert CH4 at temperatures as low as −105 °C. In situ Raman, XRD, DRIFTS analyses reveal that CH4 conversion begins with C-H cleavage followed by C-O coupling with the oxygen on IrO2. The DFT calculation results provide complemental illustration that methane dehydrogenation leads to CH2 adspecies and the subsequent C-O coupling reaction can cause formation of surface formaldehyde. Furthermore, the IrO2 (211) facet was more active than IrO2 (110) facet according to the lower reaction barriers on IrO2 (211) facet. This clearly shows that CH4 conversion on IrO2 is a structure-sensitive reaction and the results of this study can provide insights for the development of efficient catalysts for methane utilization.

References 1. Z. Liang, T. Li, M. Kim, A. Asthagiri, J. F. Weaver, Science 2017, 356, 299-303. 2. T. L. M. Pham, E. G. Leggesse, J. C. Jiang, Catal. Sci. Technol. 2015, 5, 4064-4071.

Poster Abstract 7 Christian Pomelli

Heterocyclization reactions in Ionic Liquids: A Computational Study

Cinzia Chiappea, Christian Silvio Pomellia* Raffaella Mancusob Bartolo Gabrieleb a, Department of Pharmacy – University of Pisa, Via Bonanno 33, 56126 Pisa, Italy, b, Department of Chemistry and Chemical Technologies,University of CalabriaVia Pietro Bucci, 12/C87036 – Arcavacata di Rende (Cosenza), Italy . * [email protected]

Heterocyclization reactions allow to synthesize a large number of complex organic molecules. This class of reactions can be performed using ionic liquis as reaction media with an high level of reciclabily of the media itself and of the catalyzer. Furthermore the use of ionic liquids with different anions allows to tune selectivity. The effect of the media in some of these reactions has been rationalized using DFT calculations.

References 1. R. Mancuso, C.S. Pomelli, P. Chiappetta, K.F. Gioia, A. Maner, N. Marino, L. Veltri, C. Chiappe, B, Gabriele, J. Org. Chem. accepted 2. R. Mancuso, C.S. Pomelli, F. Malafronte, A. Maner, N. Marino, C. Chiappe, B. Gabriele, Org. Biom. Chem. 2017, 15, 4831-4841. 3. R. Mancuso, C.S. Pomelli, D.S. Raut, A., N. Marino, S.V. Giofre, R. Romeo. S Sartini, C. Chiappe, B. Gabriele, ChemistrySelect 2017, 3, 894-899. 4. R. Mancuso, C.S. Pomelli, C. Chiappe, R.C. Larock, B. Gabriele, Org. Biom. Chem. 2014, 12, 651-659.

Poster Abstract 8 Eric Daiann Sosa Carrizo

Understanding the factors controlling the Migratory Insertion of saturated compounds in Au(III) complexes

E. D. Sosa Carrizo,1 J. Serra,2 X. Ribas,2 A. Amgoune,3 D. Bourissou,3 K. Miqueu1 1IPREM, Univ. Pau (UPPA). Hélioparc 2 avenue P. Angot 64053 Pau Cedex 09 (France). E-mail: [email protected]; 2QBIS-CAT, IQCC, Universitat de Girona, E-17003, Catalonia, Spain 3LHFA UMR 5069, Univ. Paul Sabatier, Toulouse Cedex 09 (France).

The Au(III) complexes present unique catalytic properties and their reactivity is far from the well known analogous of Pt(II) and Pd(II). In addition to the reductive elimination and transmetallation reactions which have been known for a long time, the ability of gold complexes to undergo oxidative addition and migratory insertion has been evidenced recently.[1] Specifically, in collaboration with D. Bourissou’s team, we described by a joint experimental-theoretical approach the insertion of olefins into Au C bonds of (P,C) cyclometallated Au(III) complexes. In order to further develop the chemistry of Au(III), it appeared important to extend this study, to satured olefins. In this context, we compared the reactivity of [(P,C)Au(III)-Ph]+ (1) and [(N,C)Au(III)-Ph]+ (2) complexes toward insertion of ethylene into Au-C bond and the reactivity of complex 1 was also evaluated experimentally and theoretically regarding the migratory insertion with (1-phenyl 2,2- difluoro)ethylene.[2],[3] In this poster, the mechanism of the migratory insertion reactions will be described using DFT calculations. Moreover, Activation Strain Model and Energy Decomposition Analysis have been used to understand the activation barriers trends in the mechanisms.

References 1. M. Joost, A. Amgoune, D. Bourissou, Angew. Chem. Int. Ed., 2015, 54, 15022-15045. 2. F. Rekhroukh, C. Blons, L. Estévez, S. Mallet-Ladeira, K. Miqueu, A. Amgoune, D. Bourissou, Chem. Sciences, 2017, 8, 4539-4545. 3. J. Serra, P. Font, E. D. Sosa Carrizo, S. Mallet-Ladeira, S. Massou, T. Parella, K. Miqueu, A. Amgoune, X. Ribas, D. Bourissou, Chem. Sciences, 2018, DOI: 10.1039/c7sc04899h.

Poster Abstract 9 Ewa Natalia Sziapa

Predictive Methane Activation by Alternant N2Y2 (Y = O, S) Ring Cations

Ewa N. Szlapaa*, Xabier Lopeza, Jesus M. Ugaldea a, UPV/EHU, Facultad de Química, Paseo de Manuel Lardizabal 3, 20080 Donostia/San Sebastian, Spain. * Presenting and corresponding author: [email protected]

Activation of methane, which is an abundant source of carbon for chemical commodities, is one of main challenges faced by modern catalysis. Even though high stability of this compound makes it extremely difficult to functionalize, chemists continue to investigate possible strategies for direct methane valorization [1]. Recently ring-like aluminium-oxide cluster cation was proven (both experimentally and theoretically) to be able to activate methane in room temperature [2]. The reaction follows proton-coupled electron transfer (PCET) mechanism rather than more conventional hydrogen-atom transfer (HAT). This discovery inspired us to explore a putative pathway leading to the cleavage of carbon-hydrogen bond in methane by alternant N2Y2 (Y = O, S) radical cations (Figure 1). These species were investigated previously in our group [3]. The potential energy surface of the predicted reaction was studied employing the tools of computational chemistry: density functional theory and coupled cluster singles and doubles with perturbative triples. The preliminary results suggest that the studied clusters may indeed be able to activate methane however following HAT pathway.

•+ •+ Figure 1 Structure of (a) N2S2 and (b) N2O2 rings. References 1. A. I. Olivos-Suarez, À. Szécsényi, E. J. M. Hensen, J. Ruiz-Martinez, E. A. Pidko, J. Gascon, ACS Catal. 2016, 6, 2965−2981. 2. J. Li, S. Zhou, J. Zhang, M, Schlangen, T. Weiske, D. Usharani, S. Shaik, H. Schwarz, J. Am. Chem. Soc. 2016, 138, 7973−7981. 3. J. M. Mercero, X. Lopez, J. E. Fowler, J. M. Ugalde, J. Phys. Chem. A, 1997, 101, 5574- 5579.

Poster Abstract 10 Gregor Simm

Automated Exploration of Chemical Reaction Networks with Full Error Control

Gregor N. Simma,* and Markus Reihera a, ETH Zurich, Laboratory of Physical Chemistry, Vladimir-Prelog-Weg 2, 8093 Zurich, Switzerland. * Presenting or corresponding author: [email protected]

For the accurate prediction of the product distribution of chemical reactions, a reaction network consisting of all relevant intermediates and elementary reactions is necessary. The complexity of such a network may grow rapidly, in particular, if reactive species (e.g., strong acids) are involved that might cause a myriad of side reactions. Therefore, only the expected, dominant reaction paths of a chemical reaction network (e.g., a catalytic cycle) are usually explored in practice. In addition, conformational diversity, which is essential for the understanding of catalytic processes, is rarely taken into account. Furthermore, the uncertainty associated with a computational result is often neglected. However, for a truly predictive theoretical investigation, a robust protocol, automation, and error control are mandatory.

We present a computational protocol and its implementation, called Chemoton, that constructs such networks in an automated manner.[1,2] For each intermediate, conformers are generated and selected based on structural similarity and energy criteria. Pairs of conformers are placed in a virtual flask and reactive complexes are formed between them by applying heuristic rules derived from conceptual electronic-structure theory. With a constrained geometry optimization employing quantum-chemical methods, activation barriers are overcome and new intermediates are formed. This procedure is followed by a transition state search. In addition, error estimates are provided for each computational result.[3,4]

We demonstrate not only the infrastructure necessary for handling such large amounts of data but also a graphical user interface for visualization and manipulation of the reaction network. With this framework, a comprehensive picture of the chemical process can be obtained and further studies (e.g., kinetic analyses) can be performed.[5] We demonstrate our approach at the example of the formose reaction,[6] an autocatalytic oligomerization reaction of formaldehyde.

References

[1] M. Bergeler, G. N. Simm, J. Proppe, M. Reiher, J. Chem. Theory Comput. 2015, 11, 5712–5722. [2] G. N. Simm, M. Reiher, J. Chem. Theory Comput. 2017, 13, 6108–6119. [3] G. N. Simm, M. Reiher, J. Chem. Theory Comput. 2016, 12, 2762–2773. [4] G. N. Simm, M. Reiher, in preparation. [5] J. Proppe, T. Husch, G. N. Simm, M. Reiher, Faraday Discuss. 2016, 195, 497–520.

Poster Abstract 11 Jean-Marc Sotiropoulos

Poster Abstract 12 Jen-Shiang K. Yu

Poster Abstract 13 Karinne Miqueu

Poster Abstract 14 Ljiljana Pavlovic

Rhodium-Catalyzed Hydrocarboxylation: Mechanistic Analysis Reveals Unusual Transition State for Carbon–Carbon Bond Formation

Ljiljana Pavlovica, Janakiram Vaitla b, Annete Bayerb and Kathrin H.Hopmannb a, Hylleraas Centre for Quantum Molecular Sciences, Department of Chemistry, UiT The Arctic University of Norway b, Department of Chemistry, UiT The Arctic University of Norway * [email protected]

The mechanism of rhodium-COD-catalyzed hydrocarboxylation of styrene-derivatives and α,β-unsaturated carbonyl compounds with CO2 has been investigated using density functional theory (PBE-D2/IEFPCM).1 The calculations support a catalytic cycle as originally proposed by Mikami and coworkers including β-hydride elimination, insertion of the unsaturated substrate into a rhodium-hydride bond and subsequent carboxylation with 2 CO2. The CO2 insertion step is found to be rate-limiting. The calculations reveal two interesting aspects: Firstly, during C-CO2 bond formation, the CO2 molecule interacts with neither the rhodium complex nor the organozinc additive. This appears to be in contrast to other CO2 insertion reactions, where CO2-metal interactions have been predicted. Secondly, the substrates show an unusual coordination mode during CO2 insertion, with the nucleophilic carbon positioned up to 3.6 Å away from rhodium. In order to understand the experimentally observed substrate preferences, we have analyzed a set of five alkenes: an α,β-unsaturated ester, an α,β-unsaturated amide, styrene and two styrene-derivatives. The analysis of the free energies shows that the ester has the lowest barrier (14.4 kcal/mol), whereas the highest activation energy was found for the amide (19.8 kcal/mol). This indicates that the barrier for CO2 insertion could explain why esters are the preferred substrates and amides are unreactive. In addition, we find that for the five studied substrates, the energetically lowest-lying TS geometries all show an unusual coordination mode of the substrate through the phenyl ring instead of the nucleophilic carbon. The overall insights may be relevant for the design of future hydrocarboxylation catalysts.

References

[1] Pavlovic, Ljiljana; Vaitla, Janakiram; Bayer, Annette; Hopmann, Kathrin Helen.“Rhodium-Catalyzed Hydrocarboxylation: Mechanistic Analysis Reveals Unusual Transition State for Carbon–Carbon Bond Formation.” Organometallics 2018. ISSN 0276- 7333.DOI: 10.1021/acs.organomet.7b00899 [2] Kawashima, S.; Aikawa, K.; Mikami, K. “Rhodium-Catalyzed Hydrocarboxylation of Olefins with Carbon Dioxide.” Eur. J. Org. Chem. 2016, 3166-3170. 45

Poster Abstract 15 Lluís Artús Suàrez

Computational study on the iron-catalyzed hydrogenation of amides to methanol and amines

Lluis Artus,* Ainara Nova, David Balcells, Mats Tilset Hylleraas Centre for Quantum Molecular Sciences, University of Oslo, Sem Sælands vei 26, Oslo [email protected]

CO2 is abundant, cheap, non-flammable and has low toxicity, making it an ideal renewable carbon feedstock. Recently, the conversion of CO2 to methanol was performed in a one-pot reaction with a ruthenium bifunctional catalyst, in the presence of amines.[1] The participation of amides as intermediates in the mechanism of this reaction prompted us to study their reduction to methanol, with the aim of developing a rational approach to the design of more active and robust catalytic systems.

In this work, the mechanism for the hydrogenation of formanilide and dimethyl formamide (DMF) to methanol with an iron catalyst (Figure) has been studied with a DFT method and compared to the experimental results of Bernskoetter and Hazari.[2] The microkinetic models derived from the DFT calculations reproduced the high conversions obtained with formanilide and the need of using the latter as co-catalyst in the hydrogenation of DMF. The computational studies revealed a complex reaction network arising from three consecutive processes; namely 1) the hydrogenation of the amide C=O bond, 2) the protonolysis of the C–N bond of an hemiaminal intermediate and 3) the hydrogenation of formaldehyde. Interestingly, the mechanism of process 2) depends on the nature of the substrate.

Figure. Reaction mechanism postulated for the iron-catalyzed hydrogenation of amides. References [1] M. S. Sandford et. al., J. Am. Chem. Soc. 2015, 137, 1028-1031. [2] N. Hazari, W. H. Bernskoetter et. al., Organometallics, 2017, 36, 409-416.

Poster Abstract 16 Manuel A. Ortuño

Heterogeneous Pd–Phosphine Interfaces for Selective Decarbonylation of Fatty Acids to α-Olefins

Manuel A. Ortuño*, Núria López Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16, 430070 Tarragona, Spain [email protected]

Transition metal nanoparticles are active for a wide range of catalytic processes, but they may lack selectivity. Current efforts are devoted to the functionalization of such surfaces with ligands to merge the robustness of heterogeneous catalysts with the selectivity of homogeneous counterparts.

Herein we employ ligand-decorated metal surfaces for the deoxygenation of biobased substrates, where selectivity is a key factor to obtain valuable chemicals.1 In particular, Pd nanoparticles functionalized with phosphine ligands show promise for the decarbonylation of fatty acids to linear α-olefins.2 We characterize Pd–phosphine interfaces with periodic DFT and unravel the key factors that account for the enhanced selectivity experimentally observed.

References 1. G. J. S. Dawes, E. L. Scott, J. Le Nôtre, J. P. M. Sanders, J. H. Bitter, Green Chem. 2015, 17, 3231-3250. 2. A. Chatterjee, V. R. Jensen, ACS Catal. 2017, 7, 2543-2547.

Poster Abstract 17 Manussada Ratanasak

Enantioselective Hydrosilylation of Styrene Catalyzed by Pd Catalyst with Chiral Polymeric Ligands

Manussada Ratanasaka, Takeshi Yamamotob, Michinori Suginomeb, Jun-ya Hasegawaa* a Institute for Catalysis, Hokkaido University, Kita 21, Nishi 10, Sapporo, Hokkaido 001- 0021, Japan. b Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Nishikyo-ku, Kyoto 615-8510, Japan * Corresponding author: [email protected]

Abstract: Asymmetric hydrosilylation of styrene with the single-handed helical poly(quinoxaline-2,3-diyl)s or PQXs bearing chiral (R)-2-butoxymethyl liganded Pd catalyst were investigated on a theoretical basis. Initially, we have calculated electronic circular dichroism spectra (ECD) of the right-handed polymer ligand (P) and the left-handed polymer ligand (M) helices of 21 mers using simplified Tamm-Dancoff Approximation (sTDA) approach [1] compared with experiment [2]. Our computational results were able to successfully reproduce the experimental CD spectra. Then, the Chalk- Harrod and the Modified Chalk-Harrod mechanisms have been investigated by DFT calculations. The results concluded that the hydrosilylation reaction proceeds through the Chalk-Harrod mechanism. Our calculations indicated that the styrene insertion step is the stereoselective as well as enantioselective steps and the Si-C reductive elimination is the rate- determining step. Moreover, we have studied the effect of helix environments using the ONIOM2 (B97XD/6-31G(d), SDD(Pd) // PM6) approach. We have found that the stereoselectivities were controlled by the conformation of styrene substrate is coordinated to Pd. The results suggested that the styrene interacts with P21S on the si side and M21R on the re side is stable. Hence, the chirality of the enantioselective products is determined by this point. In addition, the interaction between the active site part and helix environments have a significant effect on the helix stability. Our calculations results were consistent with the experimental results [3] which revealed that P helix gave an enantioenriched hydrosilylation product with the S configuration and M helix gave the R product selectively.

Figure 1 Schematic representation of the favored active sites of P21S at the RDS step and our calculated ECD spectra of 21-PQXs mers.

References 1. S. Grimme, J. Chem. Phys., 2013, 138, 244104-14. 1. T. Yamada, Y. Nagata, M. Suginome, Chem. Commun., 2010, 46, 4914-4916. 2. T. Yamamoto and M. Suginome, Angew. Chem. Int. Ed., 2009, 48, 539-542.

Poster Abstract 18 Marc Obst

Poster Abstract 19 Maren Podewitz

Associative or Dissociative? Elucidating the Olefin Metathesis Mechanism of a Cationic Molybdenum Catalyst

Maren Podewitza*, Klaus R. Liedla, Michael R. Buchmeiserb a: Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, Austria b: Institute of Polymer Chemistry, University of Stuttgart, Germany * [email protected]

Synthesis of highly functionalized polymers is an ultimate goal in chemistry because it allows for design of materials with tailored properties. Molybdenum catalysts (e.g. of the Schrock type) have successfully been used for metathesis reactions, including polymerization of olefins, but these catalysts are very sensitive to functional groups at the monomers. However recently, an N-heterocyclic carbene Mo-alkylidene catalyst has been reported that does tolerate functional groups and polymerizes olefins with hydroxyl or carbonyl functionalities.1 Density functional theory investigations were used in combination with experimental studies to unravel the olefin metathesis reaction mechanism of this new catalyst generation. Initial studies point towards a substrate dependence of the mechanism. For the 2-vinylanisole monomer, a coordination of the substrat to to the neutral catalysts – yielding a stable adduct – is found, followed by a dissociation of one (triflate) ligand to form the catalytically active cationic catalyst, thus, suggesting an associative mechanism. For the bicyclo[2.2.1]hept-5-en-2-carbaldehyd monomer on the other hand, one (triflate) ligand dissociates and the substrate coordinates, directly forming the catalytically active cationic catalyst, hence, indicating a dissociative mechanism.2

References 1. M. R. Buchmeiser, S. Sen, J. Unold, W. Fey, Angew. Chem Int. Ed. 2014, 53, 9384. 2. Manuscript in Preparation.

Poster Abstract 20 Marie Noelle Poradowski

Ethylene-Butadiene Copolymerization: A Computational Exploration of Catalysts Selectivities

Marie-Noëlle Poradowskia, Islem Belaidb, Samira Bouaoulia, Hajar Nsiria, Franck D’Agostob, Julien Thuilliezc, Christophe Boissonb, Lionel Perrina* a, Université de Lyon, CPE Lyon, INSA Lyon, ICBMS, CNRS UMR 5246, Equipe ITEMM, 43 Bd. du 11 Novembre 1918, 69622 Villeurbanne, France, b, Université de Lyon, Univ. Lyon 1, CPE Lyon, CNRS UMR 5265, C2P2, Equipe LCPP, 43 Bd du 11 Novembre 1918, F-69616 Villeurbanne, France. c, MFP Michelin, 23 Pl. des Carmes Dechaux, 63040 Clermont-Ferrand, France * Presenting author: [email protected]

The incorporation of unsaturated groups in the polyolefins confers specific properties to the material, which can be further functionalized or vulcanized. Among the different strategies to achieve such structures, the copolymerization of ethylene and butadiene catalyzed by noedymocene catalysts in chain transfer condition is very appealing. Computational mechanistic exploration at the DFT level allows to rationalize the role of neodymocene or chain transfer agent structure on synthetized polymers. Copolymerization catalysis of ethylene with butadiene mediated by neodymocenes 1 and 2 lead to different polymer microstructures that include linear, branched and cyclic units. [1] (Figure 1, left) Moreover, the polymerization of ethylene catalyzed by neodymocenes 1 or 2 in presence of dialkenymagnesium leads to formation of formation of vinyl or ring chain ends. [2] (Figure 1, right)

Figure 1. Copolymerization of ethylene with butadiene and homopolymerization of ethylene catalyzed by neodymocene catalysts in chain transfer condition.

References 1. H. Nsiri, I. Belaid, P. Larini, J. Thuilliez, C. Boisson, L. Perrin, ACS Catalysis 2016, 6, 1028. 2. I. Belaid, M.-N. Poradowski, S. Bouaouli, J. Thuilliez, L. Perrin, F. D’Agosto, C. Boisson 10.1021/acs.organomet.8b00127

Poster Abstract 21 M. B. Yeamin

Structure and reactive features of organic and organometallic catalysts for the synthesis of polyketones and organic carbonates from carbon oxides

M. B. Yeamin1, A. Aghmiz2, A. M. Masdeu1 and M. Reguero1,* 1Universitat Rovira i Virgili, Departament de Química Física i Inorgànica, C. Marcel·lí Domingo 1, 43007-Tarragona, Spain2 Faculté des Sciences, University Abdelmalek Essaadi, Mhannech II, B.P. 2121, 93030 Tétouan, Morocco *Mar Reguero e-mail address: [email protected] The energy and chemical industries are nowadays very much oil dependent, whose productions are gradually declining since 2008 and there are concerns about their future availability. Oxides from carbon (CO and CO2) are increasingly seen as attractive potential feedstocks for fuels and chemicals. Furthermore, the need of decreasing the emissions of greenhouse gas CO2 in the atmosphere is a promoting research in the area of CO2 transformation. The main drawback is its thermodynamic stability and kinetic inertness. To overcome high kinetic barrier, catalysts or highly reactive substrates are often needed. For example, epoxides react with CO2 in the presence of a catalyst to form cyclic carbonates or polycarbonates (Scheme 1).

Scheme 1. a) Cycloaddition and b) copolymerization of CO2 and epoxides

The cost in time and resources for the synthesis of new catalysts make worth the use of all possible tools to ensure the success of any proposal. The state of development of computational chemistry makes it a very useful tool to help in the development of catalysts for specific needs. It can provide information about the structure of the active catalyst and about the mechanism of the reaction of interest, and this knowledge can be used to predict the most promising catalysts prior to their synthesis. In spite of the size of the systems and the complexity of the reactions this filed has to deal with Density Functional Methods (i.e., DFT) which provide very satisfactory results.

We present here some examples of the synergy of experimental and computational methods in the development of catalysts for CO and CO2 utilization. They will comprise some examples of organometallic catalysts to obtain polyketones and organic carbonates [1-3], and some results on natural organic catalysts that present promising potentialities to obtain cyclic carbonates from CO2 and alkenes in one-pot reactions. They have the added advantage to receive from vegetable wastes, in particular from sugarcane bagasse, which leads to a green route.

References [1] A. Campos-Carrasco, C. Tortosa-Estorach, A. Bastero, M. Reguero, A. M. Masdeu-Bultó, G. Franciò, W. Leitner, A. D’Amora and B. Milani, Organometallics 2011, 30, 6572. [2] A. Campos-Carrasco, M. Bruce, M. Reguero, A. M. Masdeu-Bultó, Inorg. Chim. Acta 2014, 409, 285. [3] L. Cuesta-Aluja, A. Campos-Carrasco, J. Castilla, M. Reguero, A. M. Masdeu-Bultó, A. Aghmiz, J. CO2 Utilization 2016, 14, 10. 52

Poster Abstract 22 Nitish Govindarajan

Understanding Solvent Effects in Homogeneous Ru Catalyzed Methanol Dehydrogenation Reactions

Nitish Govindarajana*, Vivek Sinhab, Bas de Bruinb, and Evert Jan Meijera a, Amsterdam Center for Multiscale Modeling and Van ‘t Hoff Institute for Molecular Sciences, Science Park 904, 1098XH, Amsterdam, The Netherlands b, Homogeneous, Supramolecular and Bio-inspired Catalysis, Van ‘t Hoff Institute for Molecular Sciences, Science Park 904, 1098XH, Amsterdam, The Netherlands * Presenting or corresponding author: [email protected]

Development of a hydrogen economy is a promising path to address increasing global energy needs. Methanol dehydrogenation is an important reaction in this regard. Homogeneous molecular catalysts offer high selectivity and activity under ambient conditions to realize these conversions in an efficient manner. To develop active catalysts for these reactions, it is of prime importance to have a detailed and accurate understanding of the mechanism and energetics of the catalytic cycle under realistic conditions. In this work, we use density functional theory based molecular dynamics simulations (DFT-MD) with an explicit description of the solvent to gain detailed mechanistic insights on the C-H activation and hydrogen production steps during methanol dehydrogenation, catalyzed by a ruthenium based PNP pincer complex [1]. Solvent significantly affects reaction barriers and the overall mechanism, compared to previous gas-phase models [2,3]. Our results illustrate the importance of the explicit role of solvent in catalytic reaction steps, and the need of incorporating them for realistic modelling of such processes.

Figure 1: Effect of explicit solvent on methanol oxidation and hydrogen production steps catalyzed by a Ru(PNP) complex (inset)

References

[1] M. Nielsen, E. Alberico, W. Baumann, H.-J. Drexler, H. Junge, S. Gladiali, and M. Beller, Nature 495, 85 (2013) [2] X. Yang, ACS Catal. 4, 1129 (2014) [3] E. Alberico, A. J. J. Lennox, L. K. Vogt, H. Jiao, W. Baumann, H.-J. Drexler, M. Nielsen, A. Spannenberg, M. P. Checinski, H. Junge, et al., J. Am. Chem. Soc. 138, 14890 (2016)

Poster Abstract 23 Pablo Garrido

The Role of Single Electron Transfers in Copper-Based Water Oxidation Catalysis

Pablo Garrido-Barrosa, Ignacio Funes-Ardoiza, Antoni Llobeta,b*, Feliu Maserasa,b* a, Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Avgda. Països Catalans, 16, 43007 Tarragona, Spain b, Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Spain * Presenting or corresponding author: [email protected]

Water oxidation to molecular oxygen is a key reaction on the development of new sustainable technologies for energy production.1 Particularly, this reaction is one of the two redox half- reactions involved in the more general process known as artificial photosynthesis, which aims the generation of clean fuels from water and sunlight. However, water oxidation features a complex mechanistic scenario with multiple steps of bond breaking-formation and the release of four electrons. In order to overcome the resulting kinetic barriers, current research is focused on the development of new catalysts with an increasing interest on abundant first row transition metals. In this sense, revealing the operating mechanism at molecular level is an important tool for the rational desing of more active catalysts.2

Our work focuses on the computational study of the oxygen-oxygen bond formation mechanism catalysed by three different copper complexes.3-5 Initial proposals were based on the knowledge generated for Ruthenium molecular catalysts, whose development has been more extense over the years. However, the different redox features of both metals impose the need to explore new alternatives. Beside the structural differences of the three studied copper complexes, we have found a common reaction scheme based on two Single Electron Transfers (SET), in contrast to the concerted two-electron Water Nucleophilic Attack (WNA) that usually operates in single-site Ruthenium catalysts (Scheme 1). Interestingly, the so- called Single Electron Transfer-Water Nuclophilic Attack (SET-WNA) involves low kinetic barriers and electronically similar intermediates for the three copper complexes. Finally, we have further demonstrated that this new mechanism is highly disfavoured in a well-stablished Ruthenium catalyst remarking the differences between first-row and noble metal catalysts.

References 1. S. Berardi, S. Drouet, L. Francàs, C. Gimbert-Suriñach, M. Guttentag, C. Richmond, T. Stoll, A. Llobet, Chem. Soc. Rev. 2014, 43, 7501–7519 2. I. Funes-Ardoiz, P. Garrido-Barros, A. Llobet, F. Maseras, ACS Catal. 2017, 7, 1712-1719. 3. S. M. Barnett, K. I. Goldberg, J. M. Mayer, Nature Chem. 2012, 4, 498-502. 4. T. Zhang, C. Wang, S. Liu, J.-L. Wang, W. Lin, J. Am. Chem. Soc. 2014, 136, 273-281. 5. P. Garrido-Barros, I. Funes-Ardoiz, J. Benet-Buchholz, F. Maseras, A. Llobet, J. Am. Chem. Soc. 2015, 137, 6758. 54

Poster Abstract 24 Paul Meister

A Multiscale Computational Study Into the Catalytic Mechanism of NicF, a non Zn(II)-Dependent Amidase

Paul Meistera, Bogdan Iona, James W. Gaulda* a, Department of Chemistry and Biochemistry: University of Windsor, 401 Sunset Ave., Windsor, Ontario, Canada * Presenting or corresponding author: [email protected]

Abstract text: Vitamin B3 is a critical precursor to the energy generation pathways found within all living organisms. Maleamate amidohydrolase, NicF, is a key amidohydrolase involved in the metabolism of this important cofactor. In particular, it catalyzes the conversion of maleamate to maleate, producing a molecule of ammonia without the use of an active site metal ion as observed in nicotinamidase or thermolysin. Here, we employed a multiscale computational approach to examine the catalytic mechanism and substrate binding with emphasis on oxyanion hole formation. Specifically, we used molecular dynamics (MD), quantum mechanics/molecular mechanics (QM/MM), and QTAIM methods. The mechanism proceeds via a two-stage, nucleophilic addition-elimination reaction whereby initial formation of a thioester intermediate occurs followed by release of ammonia and subsequent hydrolysis to produce maleate. Nucleophilic attack by the entering water molecule in the second stage is found to be the rate-determining step with a barrier of 97.6 kJ mol-1. Stabilization of the carbonyl oxygen by the oxyanion hole is vital for the reaction to proceed, especially by HN-Thr146 and HO-Thr146. Furthermore, O=Ala145 is found to assist in the positioning of ammonia and water by forming a consistent and strong H-bond. Together, the results suggest how a non-metallo amidohydrolase can catalyze the loss of ammonia with the same Asp-Lys-Cys catalytic triad.

Poster Abstract 25 Toni Bauzá

Poster Abstract 26 Verônica Maria do Nascimento

Tellurium compound as a catalytic in synthesis of dimetilsulfide

Verônica Maria do Nascimento*, Cleverson Princival, Alcindo A. dos Santos, Ataualpa A. C. Braga Instituto de Química –USP. - São Paulo SP-Brasil *[email protected]

In this work we study computationally the mechanism for production of diphenyl 1 disulfide through the reaction between (R1)(R2)TeCl2 and thiophenol, Scheme 1-a . Interestingly, we observed an unusual catalytic role played by tellurium compounds in some of the studied processes.

Figure 1: a) Overall reaction between (R1)(R2)TeCl2 (1) and thiophenol (2) in DMSO; b) Reaction between R1TeR2, DMSO and HCl; c)Main transition states, calculated at SMD-M06L/6-31+G(d,p) level of theory, along the energy profile for reaction of 1 with 2 to produce 4. The selected bond distances are in Angstrom (Å) and the potential energies are in kcal.mol-1.

The calculated reaction mechanism is very complex, going from several steps to generate the S-S bond, Figure 1-c. In the initial step, the thiophenol approaches to the 1 to form the TS1 .5 kcal.mol-1). So, takes place the deprotonation of thiophenol through the TS2 (-0.4 kcal.mol-1). In the sequence, a second molecule of thiophenol approaches to the metal center, forming TS3 (2.0 kcal.mol-1), a concerted mechanism involving simultaneously the formation of a second S-Te bond and the deprotonation of the thiophenol via chloride. TS4 (23.0 kcal.mol-1) represents the tellurium sphere of coordination with two Te-SPh bonds. To produce 4, it is required that occurs an isomerization from trans to cis conformation via TS5 (35.0 kcal.mol-1). To rationalize the presence of dimetilsulfide as a byproduct, we proposed a parallel reaction between R1-Te-R2 (Scheme 1-b), DMSO and HCl. This step takes place through TS6 (-2.1 kcal.mol-1) and leads to the formation of water and restores 1.

The computational results are in full agreement with the experimental results to formation of disulfide catalyzed in presence of 1.

Reference

1. Zaccaria F, Wolters LP. 2016. doi:10.1002/jcc.24383. 57

Poster Abstract 27 Victor Hugo Menezes da Silva

Investigating Mechanism for the Oxidative Addition of Arenediazonium Salts to Palladium(0) and N,N ligands: A Computational Study

Vitor H. Menezes da Silva*a, Ataualpa A. C. Bragab, Carlos R. Duarte Correiaa aUNICAMP, Chemistry Institute, Department of Organic Chemistry, Campinas, SP, Brazil bUSP, Chemistry Institute, Department of Fundamental Chemistry, São Paulo, SP, Brazil *[email protected]

Oxidative addition of organic electrophiles constitutes a crucial step in many cross-coupling reactions. In this context, the Heck-Matsuda reactions involving arenediazonium salts as electrophiles have been emerged as reliable alternatives to aryl halides due them highly reactivity and synergism when employing N,N ligands.1 We described herein a new computational study on the mechanism of oxidative addition step of diazonium to palladium(0) using calculations based on DFT methods. The results showed the reaction pathway as very exergonic and presumably irreversible step, with small reaction barriers demonstrating the high reactivity of arenediazonium cation. Furthermore, a multistep mechanism is shown as feasible one, in which the first stage consists in the attack of diazonium cation to palladium(0) forming the nitrogen-palladium bond. The second stage is an isomerization of three- and four-center intermediates. Finally, the breaking of the nitrogen-aryl and formation of the aryl-palladium bond happens by a concomitant rearrangement (Figure 1). These findings are in contrast with the well-known concerted mechanism for the oxidative addition of aryl halides.2

Figure 1. Free energy profile (298.15 K in kcal/mol) of mechanism for oxidative addition of diazonium cation to palladium(0) with a N,N ligand. M06 density functional was performed with 6-31+G(d,p) basis set for lighter atoms and SDD relativistic pseudopotential basis set method for palladium. Solvent corrections were introduced via the SMD continuum solvation model.

References 1. J.de Oliveira Silva, et. al. J. Org. Chem., 2016, 81, 2010–2018. 2. V. H. Menezes da Silva, et. al. Organometallics, 2016, 35, 3170-3181 58

Poster Abstract 28 Víctor Polo

Ir(III) catalysts for CO2 fixation using silanes: DFT mechanistical studies

Víctor Poloa * a, Departamento de Química Física and Instituto de Biocomputación y Física de los Sistemas Complejos (BIFI), Universidad de Zaragoza. Pl. S. Francisco S/N 50009 Zaragoza, Spain. * Presenting or corresponding author: [email protected]

Utilization of CO2 as feedstock has the advantages that the gas is naturally occurring, abundant, and inexpensive. However, the activation of CO2 represents a challenge for chemists because of its thermodynamic and kinetic stability. In this context, the low reactivity of CO2 can be overcome by catalytic activation and functionalization. In this work, a detailed analysis on the reaction mechanism is provided using DFT calculations for Ir(III) complexes bearing triflate[1] or trifluoroacetate[2] ligands which have been experimentally tested. Examination of possible pathways includes inner vs outer sphere mechanisms, metal-ligand cooperative bond activation. Electronic and steric effects on the key steps of the catalytic cycle are discussed.

References 1. R. Lalrempuia, M. Iglesias, V. Polo, P. J. Sanz Miguel, F. J. Fernández-Alvarez, J. J. Pérez- Torrente, L. A. Oro, Angew. Chem. Int. Ed. 2012, 51, 12824-12827. 2. A. Julián, J. Guzmán, E. A. Jaseer, F. J. Fernández-Alvarez, R. Royo, V. Polo, P. García- Orduña, F. J. Lahoz, L. A. Oro, Chemistry, Eur. J. 2017, 23, 11898-11907.

Poster Abstract 29 Wen-Jie Wei

Mechanism of the Dinuclear Iron Enzyme p-Aminobenzoate N- oxygenase from Density Functional Calculations

Wen-Jie Wei,a Per E. M. Siegbahn,b Rong-Zhen Liao*a a, Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica, Hubei Key Laboratory of Materials Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China b, Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, SE-10691 Stockholm, Sweden

*Corresponding author: [email protected]

AurF is a diiron enzyme that utilizes two dioxygen molecules as the oxidant to catalyze the oxidation of p-aminobenzoate to p-nitrobenzoate. Density functional calculations were performed to elucidate the reaction mechanism of this enzyme. Two different models were considered, with the oxygenated intermediate being a diferric peroxo species or a diferric hydroperoxo species. The calculations strongly favor the model with a diferric peroxo species and support the mechanism proposed by Bollinger and co-workers.[1] The reaction starts with the binding of a dioxygen molecule to the diferrous center to generate a diferric peroxide complex. This is followed by the cleavage of the O-O bond, in concomitant with the formation of the first N-O bond, which has a barrier of only 9.2 kcal/mol. Subsequently, the first-shell ligand Glu227 abstracts a proton from the substrate. After the delivering of two electrons from external reductant and two protons from solution, a water molecule and the experimentally suggested intermediate p-hydroxylaminobenzoate are produced and the diferrous center is regenerated. The oxidation of the p-hydroxylaminobenzoate intermediate requires the binding of a second dioxygen molecule to the diferrous center to generate the diferric peroxide complex. Similarly to the oxidation of p-aminobenzoate, the O-O bond cleavage and the formation of the second N-O bond take place in a concerted step. The p- nitrobenzoate product is formed after the release of two protons and two electrons from the substrate. For the model with a hydroperoxo species, our calculations showed that the total barrier for the substrate oxidation is very high, being over 40 kcal/mol due to the large energy penalty for the generation of the active hydroperoxo species from a more stable complex with a bridging peroxide and a protonated substrate amino group.

References 1. Li, N.; Korboukh, V. K.; Krebs, C.; Bollinger, J. M. Proc. Natl. Acad. Sci. U.S.A. 2010, 107, 15722.

Poster Abstract 30 Ying-Ying Li

Mechanism of Water Oxidation Catalyzed by a Mononuclear Iron Complex with a Square Polypyridine Ligand: A DFT Study

Ying-Ying Lia, Rong-Zhen Liaoa* aSchool of Chemistry and Chemical Engineering, Huazhong University of Science&Technology, Wuhan, Hubei Province, China, 430074 *Presenting author: [email protected]

III + The mononuclear complex 1Cl[Cl−Fe (dpa)−Cl] has been reported to catalyze water oxidation in pH=1 aqueous medium with ceric ammonium nitrate as a chemical oxidant. The mechanism of oxygen evolution driven by this catalyst was investigated via density

functional calculations. The results showed that one chloride ligand of 1Cl has to exchange III 2+ with a water molecule to generate 1[Cl−Fe (dpa)−OH2] as the starting species of the catalytic cycle. The initial one-electron oxidation of 1 is coupled with the release of two protons, generating 2[Cl−FeIV(dpa)=O]+. Another one-electron transfer from 2 leads to the formation of an FeV=O complex 3[Cl−FeV(dpa)=O]2+, which triggers the critical O−O bond formation. The electronic structure of 3 was found to be very similar to that of the high-valent heme-iron center of P450 enzymes, in which a π-cation radical ligand is believed to support a formal iron(IV)-oxo core. Two competing pathways were suggested for the O−O bond formation. One is the nitrate nucleophilic attack on the iron(V)-oxo moiety with a total barrier of 12.3 kcal mol−1. In this case, nitrate functions as a co-catalyst for the dioxygen formation. The other is the water nucleophilic attack on iron(V)-oxo with a greater barrier of 16.5 kcal mol−1. In addition, ligand degradation via methyl hydrogen abstraction was found to have a barrier similar to the O−O bond formation, while the aromatic carbon hydroxylation has a higher barrier.

References 1. L. D. Wickramasinghe, R. Zhou, R. Zong, P. Vo, K. J. Gagnon, R. P. Thummel, J. Am. Chem. Soc. 2015, 137, 13260-13263. 2. Y.-Y. Li, L.- P.Tong, R.- Z. Liao, Inorg. Chem. 2018, 57, 4590-4601

Poster Abstract 31 Ya-Qiong Zhang

Reaction Mechanism of Hydrogen Evolution Catalysed by Co and Fe Complexes Containing a Tetra-dentate Phosphine Ligand – A DFT Study

Ya-Qiong Zhanga, Rong-Zhen Liaoa* a, School of Chemistry and Chemical Engineering, Huazhong University of Science & Technology, Wuhan, 430074, China, *Email: [email protected]

Abstract The reaction mechanism of the electro-catalytic proton reduction in neutral phosphate buffer enabled by mononuclear cobalt and iron complexes containing a tetra-dentate 1 phosphine ligand (MP4N2, M=Fe, Co) has been elucidated by density functional calculations. The phosphate from the buffer was found to play a crucial role by replacing H2O to phosphate. For CoP4N2, the mechanism involves two sequential proton-coupled electron transfer reductions with calculated reduction potentials of -0.58 V and -0.72 V, respectively. Followed by H–H bond formation, which takes place via the coupling of the CoII-H and the proton from the dihydrogen phosphate ligand. The total barrier was calculated to be 18.2 kcal mol-1 with an applied potential of -0.5 V, which can further decreased to only 11.2 kcal mol-1 with an applied potential of -0.8 V. When the phosphate is displaced by a water molecule, the total barrier for the dihydrogen formation increases by 11.0 kcal mol-1. For the iron catalyst, the overall mechanism is essentially the same. The calculated results are in good agreement with the experimental data.

Reference: 1. L. Chen, M. Wang, K. Han, P. Zhang, F. Gloaguen and L. Sun, Energy Environ. Sci., 2014, 7, 329-334.

Poster Abstract 32 Mauro Fianchini

Computational study of redox-driven phosphorus catalysis: the Wittig case

Mauro Fianchini*a, Feliu Maserasa,b a, Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Avgda. Països Catalans, 16, 43007 Tarragona, Spain b, Universitat Autonoma de Barcelona, Department de Quimica, 08193 Bellaterra, Spain * Presenting or corresponding author: [email protected]

Wittig reaction is a simple way to achieve versatile olefinic blocks1. Catalytic Wittig (CW) protocols have been reported and optimized for different ylides2. Yet, synthesis alone has not been able to provide a clear and detailed explanation of the stereoselection nor to expand the versatility of Wittig catalysts to produce the desired target alkene. Computational modeling has been a prominent way of explaining Wittig diastereoselectivity in the last decade3. We hereby propose the first complete theoretical model of the CWR (figure left). This paper presents to the audience state- of-the-art approaches in modern computation (M06-2X- D3/def2-TZVP level with SMD solvation in toluene at 373 K complemented by kinetic models)4 aiming to shed definitive light on the reactivity of stabilized phosphorus ylides and to uncover the catalytic motifs behind E/Z- diasteroselective footprints in CWR. Calculated systems of kinetic laws mimic the reactivity of complex network of equilibria and elucidate important parameters like rate determining step(s), fast/slow reduction of phosphine oxide4 and E/Z-diasteroselective resolution for cycles involving catalytic species analogous to 3-methyl-1-phenyl- phospholane 1-oxide5.

References 1. G. Wittig, U. Schollkopf, Chem. Ber. 1954, 87, 1318–1330 2. C.J. O'Brien et al., Angew. Chem. Int. Ed. 2014, 53, 12907-12911 3. J. Harvey et al., J. Am. Chem. Soc., 2006, 128, 2394-2409 4. M. Fianchini, J. Org. Chem., just accepted 5. M. Fianchini, C.J. O’Brien, Encyclopedia of Reagents for Organic Synthesis, John Wiley & Sons, Ltd, 2001

Poster Abstract 33 Shaofei Ni

Poster Abstract 34 Sergi Fernández

N4 I [(L )Co -CO], the sink resting state in the electrochemical CO2 reduction process catalyzed by pyridylamino Co complexes

Sergio Fernándeza, Federico Francoa, Josep Maria Luisb*, Julio Lloret-Fillola,c* a, Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Avinguda Països Catalans 16, 43007, Tarragona, Spain. b, Institut de Química Computacional i Catàlisi (IQCC), Departament de Química, Campus Montilivi s/n, 17007, Girona, Spain. c, Catalan Institution for Research and Advanced Studies (ICREA), Lluïs Companys, 23, 08010, Barcelona, Spain. * Presenting or corresponding author: [email protected] [email protected]

In the last years, pyridine-based Co complexes have emerged as active catalysts in the CO2- to-CO reduction process under both photo- and electrochemical conditions.1 However, investigations to fully understand the reaction mechanism and to identify the limiting factors have yet to be adressed.2 We have studied the electrocatalytic CO2 reduction process mediated by a model cobalt catalyst based on the PyMe2tacn ligand (LN4).3 The combination of electrochemical and spectroscopic techniques (CV, IR-SEC), together with the computational modelling of the catalytic cycle, allowed the detection of a highly stable [LN4CoI-CO]+ intermediate as the inactive resting state in the CO2 reduction process at low overpotentials (Figure 1). To improve the catalytic performance of our system we propose the recovery of the catalytically active species via light-induced metal-carbonyl dissociation.

References 1. M. B. Chambers, X. Wang, M. Fontecave. Chem. Soc. Rev. 2017, 46, 761. 2. F. Wang, et al. Catal. Sci. Technol. 2016, 6, 7408. 3. A. Call, et al. Chem. Sci. 2018, 9, 2609.

PARTICIPANTS

Artús Suàrez, Lluís - Universitetet i Oslo Ballester, Pau - Institute of Chemical Research of Catalonia Bauzá, Antonio – University of the Baleari Islands Besora, Maria – Institute of Chemical Research of Catalonia Bo, Carles – Institute of Chemical Research of Catalonia Braga, Ataualpa A. C. – Universidade de São Paulo Carbó, Jorge J. – Universitat Rovira i Virgili Cavallo, Luigi – King Abdullah University of Science and Technology Darù, Andrea – KU Leuven Drzewiecka-Mtuszek, Agnieszka – Polish Academy of Sciences Eriksson, Lars – Materials and Environmental Chemistry Fernández, Sergi – Institute of Chemical Research of Catalonia Fey, Natalie – University of Bristol Fianchini, Mauro – Institute of Chemical Research of Catalonia Frontera, Antonio – University of the Balearic Islands Funes Ardoiz, Ignacio – Institute of Chemical Research of Catalonia Garridos Barros, Pablo – Institute of Chemical Research of Catalonia González Fabra, Joan – Institute of Chemical Research of Catalonia Govindarajan, Nitish – University of Amsterdam Harvey, Jeremy – KU Leuven Hatanaka, Miho – Nara Institute of Science and Technology Himo, Fahmi – Stockholm University Hopmann, Kathrin H. – UiT The Arctic University of Norway Jaraíz Maldonado, Martín – Universidad de Valladolid Jiao, Haijun - Leibniz-Institut für Katalyse e. V. Li, Ying-Ying – Huahzong University of Science & Technology Liao, Rong-Zhen – Huazhong University of Science and Technology Lledós, Agustí – Universitat Autònoma de Barcelona Maryasin, Boris – University of Vienna, Institute of Theoretical Chemistry 66

Mateo, Ana – Institute of Chemical Research of Catalonia Meister, Paul – University of Windsor Miqueu, Karinne – IPREM. University of Pau Nascimento (do), Veronica Maria – IQ-USP Ni, Shaofei – Institute of Chemical Research of Catalonia Norrby, Per-Ola – AstraZeneca Gothenburg Nova, Ainara – University of Oslo Obst, Marc – The Artic University of Norway Ormazábal, Rodrigo – Universidad Bernardo O’Higgins Ortuño, Manuel Ángel – Institute of Chemical Research of Catalonia Paton, Rob – University of Oxford Perrin, Lionel – Université de Lyon Pavlovic, Ljiljana – The Artic University of Norway Pérez Soto, Raúl – Institute of Chemical Research of Catalonia Petrus Pérez, Enric – Institute of Chemical Research of Catalonia Podewitz, Maren – University of Innsbruck Polo, Víctor – Universidad de Zaragoza Pomelli, Christian Silvio – University of Pisa Poradowski, Marie Noelle – Université Claude Bernard Lyon 1 Ramos, Maria Joao – Universidade do Porto Ratanasak, Manussada – Hokkaido University Ricart, Josep M. – Universitat Rovira i Virgili Salom Català, Antoni – Universitat Rovira i Virgili Sánchez Pladevall, Bruna – Institute of Chemical Research of Catalonia Sauer, Joachim – Humboldt Universität zu Berlin Schoenebeck, Franziska – RWTH Aachen University Segado Centellas, Mireia – Institute of Chemical Research of Catalonia Simm, Gregor – ETH Zurich Solé, Albert – Universitat Rovira i Virgili Sosa Carrizo, E. Daiann – CNRS-IPREM-UPPAA

Sotiropoulos, Jean-Marc – CNRS-IPREM-UPPAA Szlapa, Ewa Natalia – Universidad del País Vasco EHU Thiel, Walter – Max-Planck-Institut für Kohlenforschung Toroker, Maytal Caspary – Technion, Israel Institute of Technology Ujaque, Gregori – Universitat Autònoma de Barcelona Wei, Wen-Jie – Huazhong University of Science & Technology Yeamin, Md Bin – Universitat Rovira i Virgili Yeh, Chen-Hao – National Taiwan University of Science & Technology Yu, Jen-Shiang – Inst. of Bioinformatic & Systems Biology, Chiao Tung Univ. Zhang, Ya-Qiong – Huazhong University of Science & Technology Zhihong, Wei – Leibniz-Institut für Katalyse e. V.