BOOK OF ABSTRACTS

Tarragona, October 18-19th, 2018

Centre Tarraconense - El Seminari

Carrer Sant Pau, 4 43003 - Tarragona Catalunya - Spain

Sponsors and collaborators

PROGRAM

October 18th October 19th

8:30-9:00 Registration

9:00-9:15 Welcoming

Session 1: Santa Tecla room Session 5: Santa Tecla room

9:15-10:05 P1. J. N.H. Reek P4. J. Pérez-Ramírez

10:05-10:25 O1. E. de Jesús O17. L. M. Martínez Prieto

10:25-10:45 O2. J. A. Mata O18. G. Espino

10:45-11:15 Coffee Break

Session 2: Santa Tecla room Session 6: Santa Tecla room

11:15-11:30 O3. D. Pla O19. F. J. Fernández-Alvarez

11:30-11:45 O4. M. Besora O20. D. Pham Minh

11:45-12:00 O5. C. Fliedel O21. J. M. Asensio

12:00-12:15 O6. M. Biosca O22. J. Tejero

12:15-12:30 O7. E. Martín Morales O23. Y. Wang

12:30-12:45 O8. G. Salas O24. J. Mestre

12:45-13:00 O9. Y. Min O25. A. Pajares

13:00-14:40 Lunch & Poster session

Session 3: Sala d'actes room Session 7: Santa Tecla room

14:40-15:30 P2. T. Soós P5. A. Martínez

15:30-15:45 O10. A. M. López-Vinasco Closing and prizes

15:45-16:00 O11. A. Cunillera

16:00-16:15 O12. D. Zhang

16:15-16:30 O13. G. Olivo

16:30-17:00 Coffee break

Session 4: Sala d'actes room

17:00-17:15 O14. A. Casitas

17:15-17:30 O15. N. Romero

17:30-17:45 O16. S. Sierra

17:45-18:35 P3. M. Robert

20:30 Conference Dinner

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Table of contents PLENARY LECTURES 7 P1. Supramolecular approaches to control selectivity in transition metal catalysis

Joost N.H. Reek 8 P2. Bifunctional Organocatalysis: Creation and Construction

Tibor Soós 9 P3. Molecular catalysis of CO2 reduction with Fe and Co complexes. A combined electrochemical and photochemical approach

Marc Robert 10 P4. Catalysis Engineering for Sustainable Technologies

J. Pérez-Ramírez 11 P5. Tuning the properties of cobalt nanoparticles for Fischer-Tropsch synthesis

Agustín Martínez 12 ORAL COMMUNICATIONS 13 O1. Boomerang Activation in Heck-Mizoroki Reactions Catalyzed by Bis(N-Heterocyclic Carbene)palladium Complexes

A. M. Prieto, A. Ortiz, J. C. Flores, E. de Jesús 14 O2. Dehydrogenation reactions by design of well-defined supported catalysts

C. Mejuto, A. Mollar, D. Ventura-Espinosa, P. Borja, J. A. Mata 15 O3. Palladium-mediated radical homo-coupling reactions: a surface catalytic insight

D. Pla, I. Favier, M.-L. Toro, M. Gómez 16 O4. Mechanisms of Intramolecular Insertion in Copper Catalysed Carbene Transfers

M. Besora F. Maseras 17 O5. N-Heterocyclic carbene complexes of first row transition metal complexes: synthesis, reactivity and applications

C. Fliedel, Lucas Thevenin, Jean-Claude Daran, R. Poli 18 O6. Novel approach for the synthesis of chiral tertiary α-aryl oxindoles via Pd-catalyzed decarboxylative protonation. An experimental and theoretical mechanistic investigation

M. Biosca, M. Magre, M. Jackson, P. Guiry, P.-O. Norrby, O. Pàmies, M. Diéguez 19 O7. Straightforward synthesis of hybrid nanoparticles stabilized by organophosphorous ruthenium dyes

E. Martín Morales, Y. Coppel, C. Bijani, V. Collière, P. Sutra, A. Igau, K. Philippot 20 O8. Magnetically recoverable photocatalysts based on metal oxide nanostructures

L. González, M. E. Rabanal, G. Salas 21 O9. Controlled Synthesis of Ru Nanoparticles Covalent Assemblies

Y. Min, I. C. Gerber , H. Nasrallah, D. Poinsot, J. C. Hierso, M. R. Axet, P. Serp 22 O10. Selective Hydrogenation of Alkynes into (Z)-alkenes with Nickel Nanoparticles Stabilized by Imidazolium-aminidate Ligands

A. M. López-Vinasco, L. M. Martínez-Prieto, J. M. Asensio, B. Chaudret, J. Cámpora, P. W. N. M. van Leeuwen 23

O11. Synthesis of chiral γ-aminobutyric esters via Rhodium catalysed asymmetric hydroaminomethylation of α-alkyl acrylates

A. Cunillera, C. Godard, A. Ruiz 24 O12. Synthesis of new bis(boryl)acetal compounds from CO2

D. Zhang , S. Bontemps 25 O13. Remote C-H Oxidation guided by Supramolecular Recognition

G. Olivo, G. Farinelli, A. Barbieri, O. Lanzalunga, S. Di Stefano , M. Costas 26 O14. Visible light metallaphotoredox strategies towards the cleavage of Csp3-Cl bonds

Miguel Claros, Jordi Aragón-Artigas, Felix Ungeheuer, Alicia Casitas, Julio Lloret-Fillo 27

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O15. Co3O4 nanoparticle-based dyads for light-driven water oxidation

J. De Tovar, N. Romero, S. Denisov, R. Bofill, C. Gimbert-Suriñach, D. Ciuculescu-Pradines, S. Drouet, A. Llobet, P. Lecante, V. Colliere, Z. Freixa, N. McClenaghan, C. Amiens, J. García-Antón, K. Philippot, and X. Sala 28

O16. Synthesis of pharmacologically relevant cyclobutanes by regio- and stereoselective [2+2]-photocycloadditons

S. Sierra, J.M. Mateo, M.V. Gómez, C. Cativiela, E. Gómez Bengoa, E.P. Urriolabeitia 29 O17. Selective Hydrogenation of Fatty Acids with Doped Graphene-Supported Ruthenium Nanoparticles

L. M. Martínez-Prieto, M. Puche, B. Chaudret, A. Corma. 30 O18. Developing the Hydrogen Storage Technology: Highly Efficient Dehydrogenation of Ammonia Boranes with Ru(II) Complexes Bearing 2-(2-Aminophenyl)-1H-benzimidazole

G. Espino, M. Martínez-Alonso, M. Ruiz de Castañeda, A. D. Phillips, Crystal O’Connor A. M. Rodríguez 31 O19. Iridium catalyzed functionalization of amines with CO2 and hydrosilanes

Francisco J. Fernández-Alvarez 33 O20. Dry reforming of methane over hydroxyapatite supported nickel and cobalt catalysts

D. Pham Minh, T. S. Phan, Q. Tran Thi, A. Nzihou, H. Nguyen Xuan, D. Grouset 34 O21. CO2 Methanation over Ni/SiRAlOx Catalyst using Magnetic Nanoparticles as a Magnetically-Induced Heating Source

J. M. Asensio, S. S. Kale, M. Estrader, J. Marbaix, A. Bordet, M. Werner, P. F. Fazzini, K. Soulantika, B. Chaudret. 35

O22. One-pot Butyl Levulinate Production from Fructose and Butanol over Dowex 50Wx2: Water Effect on Catalytic Activity

G. Freddi, G. Gordillo, E. Ramírez, R. Bringué, M. Iborra, J. Tejero, F. Cunill 36 O23. Oxidation catalysis under green chemistry conditions

Y. Wang, P. Guillo, D. Agustin, J.-C. Daran, E. Manoury, R. Poli 37 O24. Efficient Pentafluoroethylation of Allyl and Benzyl Halides with TMSCF3-Derived CuC2F5. Mechanistic Insights

Jordi Mestre, Sergio Castillón, and Omar Boutureira 38 O25. Study of VC-based catalysts for CO2 conversion to CO

Pajares A.Ramirez de la Piscina P., Homs N. 40 POSTERS 41 PS1. Isotopic labeling for the evaluation of drug candidates catalyzed by metallic nanoparticles

D. Bouzouita, S. Tricard, L. Martinez-Prieto, G.Lippens and B. Chaudret 42 PS2. Ensemble effect in Ru@C60 hydrogenation catalysts

C. Rivera-Carcamo, M.R. Axet, P. Serp 43 PS3. Bimetallic nanoparticles in glycerol : Structure & surface reactivity

T. Dang Bao, I. Favier, M. Gómez 44 PS4. Bio-Sourced Deep Eutectic Solvents and ScCO2: Innovative Media for Metal-Based Nanocatalysts

G. Garg, A. M. Masdeu-Bultó, Y. Medina-Gonzalez, M. Gómez 45 PS5. Stabilization of ultra-small ruthenium nanoparticles by ethanoic acid

R. González-Gómez, L. Cusinato, I. del Rosal, C. Amiens, R. Poteau, K. Philippot. 46 PS6. Remarkable catalytic activity of gel-trapped palladium nanoparticles in flow chemistry using a polymeric membrane reactor.

M.López Viveros, I. Favier, M. Gómez, J.F. Lahitte, J.C. Remigy 47 PS7. Cobalt catalysts on carbon based materials for Fischer-Tropsch synthesis

A. Ghogia, D. Pham Minh, P. Serp, K.Soulantica, A.Nzihou 48 PS8.Structure-synthesis relationship study of colloidal PdNPs using designed experiments

O.Benkirane, J. Delgado, J. Ferré, D. Curulla-Ferré, C. Claver, C. Godard 49 PS9. Synthesis of monometallic Ni, Cu, Pd and bimetallic NiCu and PdCu NPs on carbon nanotubes as nanocatalysts for selective hydrogenation reactions

Jorge A. Delgado, Diego Lomelí, Miriam Diaz de los Bernardos, Sara Perez-Rodriguez, Aitor Gual, Carmen Claver, Cyril Godard 50

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PS10. Immobilized rhodium catalysts for asymmetric hydroformylation under batch and flow conditions

Anton Cunillera, Cyril Godard, Aurora Ruiz and Carmen Claver 51 PS11. Study of THFA production from furfural using hectorite supported Ni, Cu or Ni-Cu catalysts

V. Sánchez , P. Salagre, Y. Cesteros 52 PS12. Photo-H2 Production by Nickel- and Cobalt-Metal Complexes Based on a Pyridinophane Ligand

P. Guillo, E. Giannoudis, Y. Wang, J.-C. Daran, M. Chavarot-Kerlidou, D. Agustin, V.Artero, A. G. Coutsolelos, E. Manoury, R. Poli 53

PS13. Metal-Based Nanomaterials as Catalyst for Water Splitting I. Álvarez-Prada, J. Muñoz, L. Escriche, K. Philippot, X. Sala, N. Romero, J. García-Antón 54

PS14. Co(OH)2 Nanoparticles Supported on Carbon Fibers as Electrocatalysts for the Oxygen Evolution Reaction

L. Mallón, A. Moya, R. Más-Ballesté, J. Alemán, J. García-Antón, R. Bofill, X. Sala, K. Philippot 55 PS15. Solar-driven water splitting: from molecular catalysis to photoelectrochemical cells

S. Grau, M. Ventosa, N. Jameei Moghaddam, Y. Shi, W. Cambarau, T.-Y. Hsieh, E. Palomares, M. Lanza, C. Gimbert-Suriñach and A. Llobet 56

PS16. Covalent Organic Frameworks with Manganese Carbonyl Species for CO2 Reduction. G.C. Dubed, S. S. Mondal, F.Franco, A. Shafir, J. Lloret-Fillol 57

PS17. Development of new P,S-ligands for Pd-catalyzed asymmetric allylic substitution. Theoretically guided ligand optimization.

J. Saltó, M. Biosca, J. Margalef, X. Caldentey, M. Besora, C.Rodríguez-Escrich, X. C. Cambeiro, F. Maseras, O. Pàmies, M. Diéguez, M. A. Pericàs 58

PS18. Catalytic Alkane Functionalization Via Iron-Carbene Insertion Reaction Alberto Hernán-Gómez, Miquel Costas 59

PS19. Iron Catalyzed Selective Syn-dihydroxylation of Alkenes. Catalyst Design and Elucidation of High Valent Reaction Intermediates

M. Borrell, E. Andris, J. Roithová and M. Costas. 60 PS20. After the O-O bond formation in Ru catalyzed WO: a missing link.

C.Casadevall, V. M. Diaconescu, W. R. Browne, F. Franco, N. Cabello, J. B. Buchholz, and J. Lloret-Fillol 61 PS21. A Stereoselective Domino Approach towards α,β-Unsaturated γ-Lactams

Jianing Xie, Sijing Xue, Arjan W. Kleij 62 PS22. Computational studies on phosphane-stabilized Rh and Ru nanoclusters: structure and reactivity.

A. Salom-Català, J.J. Carbó, J.M. Ricart 63 PS23. Comprehensive computational study of redox-driven Wittig catalysis

M. Fianchini, F. Maseras PS24. Copper(I)-catalyzed borylative cyclization towards bioactive carbocyclic compounds

J. Royes,S. Ni, A.Farré, E. Lacascia, J. J. Carbó, A. B. Cuenca, F. Maseras, E. Fernández 65 PS25. Metal-ligand Cooperative Catalysis with Indene based Pd and Pt Pincer Complexes

B. Martin Vaca, J. Monot, D Bourissou 66 PS26. Organo-Catalyzed Ring-Opening Reaction of epoxides with gem-Diborylalkanes.

R. Gava, E. Fernández 67 PS27.A Novel 1,4-Hydroboration reaction with 1,3-dienes. An experimental and theoretical point of view.

Ricardo J. Maza, Jordi J. Carbó, E. Fernández 68 PS28. -Lactone Production in Two-Phase Catalysis with In-Situ Extraction

M. Y. Souleymanou, C. Godard, A. M. Masdeu-Bultó, G. Francio, W. Leitner 69 PS29. Enantioselective Construction of Tertiary Sulfones via Copper-Catalyzed Propargylic Substitution

José Enrique Gómez, Àlex Cristòfol, and Arjan W. Kleij 70 PS30. Transforming CO2 into cyclic carbonate using lignocellulosic waste as catalyst: experimental and computational approach

M. B. Yeamin, M. S. El Ouahabi, A. Aghmiz, M. Reguero and A. M. Masdeu-Bultó 71

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PLENARY LECTURES

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P1. Supramolecular approaches to control selectivity in transition metal catalysis Joost N.H. Reek

Homogeneous and Supramolecular Catalysis, Van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Sciencepark 904 Amsterdam (THE NETHERLANDS). j.n.h.reek@ uva.nl.

The interface between supramolecular chemistry and transition metal catalysis has received surprisingly little attention in contrast to the individual disciplines. It provides, however, novel and elegant strategies that lead to new tools for the search of effective catalysts, and as such this has been an important research theme in our laboratories. In this presentation I will focus on supramolecular strategies to control selectivity in transition metal catalysis, which is especially important for reactions that are impossible to control using traditional catalyst development. For substrates with functional groups we use substrate orientation effects to control selectivity, whereas for non-functionalized substrates we create cages around the active transition metal. More recently, we also explored the use of large nanospheres that allows to perform catalysis at high local concentrations, leading to rate acceleration for several different reactions.

Figure: Supramolecular pre-organization to control selectivity in hydroformylation and CH activation catalysis. Nanospheres can also be used to control selectivity. References [1] For reviews see: 1) Reek et al “New directions in supramolecular catalysis,” Nature Chemistry, 2010, 2, 615. 2) Reek et al, “Transition metal catalysis in confined spaces” Chem. Soc. Rev, 2015, 44, 433 – 448 3) Reek et al , “Supramolecular control of selectivity in transition-metal catalysis through substrate preorganization” Chem. Sci, 2014, 5, 2135. 4) Reek et al.” Template ligand approach to catalyst encapsulation” Acc. Chem. Res., 2018, 10.1021/acs.accounts.8b00345

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P2. Bifunctional Organocatalysis: Creation and Construction Tibor Soós

Institute of Organic Chemistry, Research Centre for Natural Sciences, Hungarian Academy of Sciences, Budapest, 2 Magyar tudósok krt., H-1117, Hungary, soos.tibor@ttk.mta.hu

Our research program revolves around the theme of bifunctional organocatalysis, thus the

major objectives of our group are catalysts design and discovery, methodological developments and mechanistic investigations. Along this line, two key topics will be presented, the bifunctional non-covalent organocatalysis and the frustrated Lewis pair chemistry.

We have developed epi-quini(di)ne bifunctional thiourea organocatalysts as a general and efficient catalysts for a variety of asymmetric reactions. Our systematic work revealed many aspects of bifunctionality and showed also the synthetic potential of this chemistry. Most recently, we have initiated a synthetic program which exploits the potential offered by bifunctional organocatalysis to construct highly complex structures.1

Relying on the bifunctional concept, even the activation of molecular hydrogen can be realized using a unique bifunctional system, a frustrated Lewis pair (FLP). While the first generation of FLPs could be employed in metal-free hydrogenation, there were multiple synthetic limitations that inhibited the penetration of this valuable method. To avoid this limitation, we have introduced the size-exclusion structural design element in FLP chemistry and developed a unique frustrated Lewis acid-base pair catalyst having an unprecedented functional group tolerance and orthogonal reactivity.2

References [1] (a) B. Vakulya, Sz., Varga, A. Csámpai, T. Soós Org. Lett. 2005, 7, 1967. (b) A. Hamza, G. Schubert, T. Soós J. Am. Chem. Soc. 2006, 128, 13151. (c) G. Tárkányi, P. Király, Sz. Varga, B. Vakulya, T. Soós Chem. Eur. J. 2008, 14, 6078. (d) B. Vakulya, Sz. Varga, T. Soós J. Org. Chem. 2008, 73, 3475. (e) Sz. Varga, G. Jakab, L. Drahos, T. Holczbauer, M. Czugler, T. Soós Org. Lett. 2011, 13, 5416. (f) G. Tárkányi, P. Király, T. Soós, Sz. Varga Chem. Eur. J. 2012, 18, 1918. (g) B. Kótai, Gy. Kardos, A. Hamza, V. Farkas, I. Pápai, T. Soós Chem. Eur. J. 2014, 20, 5631. (h) E. Varga, L. T. Mika, A. Csámpai, T. Holczbauer, Gy. Kardos, T. Soós RSC Advances 2015, 5, 95079. (i) Sz. Varga, G. Jakab, A. Csámpai, T. Soós J. Org. Chem. 2015, 80, 8990. (j) B. Berkes, K. Ozsváth, L. Molnár, T. Gáti, T. Holczbauer, Gy. Kardos, T. Soós Chem. Eur. J. 2016, 22, 18101. (k) A. Bacsó, M. Szigeti, Sz. Varga, T. Soós Synthesis, 2017, 49, 429. [2] (a) T. A. Rokob, A. Hamza, A. Stirling, T. Soós, I. Pápai Angew. Chem. Int. Ed. 2008, 47, 2435. (b) G. Erős, H. Mehdi, I. Pápai, T. A. Rokob, P. Király, G. Tárkányi, T. Soós Angew. Chem. Int. Ed. 2010, 49, 6559. (c) G. Erős, K. Nagy, H. Mehdi, I. Pápai, P. Nagy, P. Király, G. Tárkányi, T. Soós Chem. Eur. J. 2012, 18, 574. (d) Á. Gyömöre, M. Bakos, T. Földes, I. Pápai, A. Domján, T. Soós ACS Catal. 2015, 5, 5366. (e) M. Bakos, Á. Gyömöre, A. Domján, T. Soós Angew. Chem. Int. Ed. 2017, 56, 5217. (d) É. Dorkó, B. Kótai, T. Földes, Á. Gyömöre, I. Pápai, T. Soós Angew. Chem. Int. Ed. 2017, 56, 9512.

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P3. Molecular catalysis of CO2 reduction with Fe and Co complexes. A combined electrochemical and photochemical approach

Marc Robert Laboratoire Electrochimie Moléculaire - UMR CNRS 7591, Université Paris Diderot, Sorbonne Paris Cité, 15 rue

Jean de Baïf, 75013 Paris, France, robert@univ-paris-diderot.fr.

Recent attention aroused by the reduction of carbon dioxide has as main objective the production of useful organic compounds and fuels renewable fuels in which solar energy would be stored. Molecular catalysts can be employed to reach this goal. One route consists in first converting sunlight energy into electricity that could be further used to reduce CO2 electrochemically.[1-2] Another approach is to directly use the visible photons and photo-stimulate the electrochemical reduction of the gas in the presence of an appropriate sensitizer and a sacrificial electron donor.[3-4] Molecular catalysts may provide excellent selectivity but usually with less durability and more complex processability than solid materials. Hybrid systems in which a robust molecular catalyst is associated to a porous carbon material as conductive support may combine the advantages of both homogeneous and heterogeneous catalysis [5-6]. Using Fe and Co complexes (porphyrins and quaterpyridines), our recent results will be discussed, illustrating the synergy between electrochemical and photochemical approaches and the rich potential of molecular catalysts to generate fuels from CO2 used as a renewable feedstock. References [1] S. Drouet, C. Costentin, M. Robert, J-M. Savéant, Science, 2012, 338, 90-94. [2] I. Azcarate, C. Costentin, M. Robert, J-M. Savéant, J. Am. Chem. Soc., 2016, 138, 16639-16644. [3] Z. Guo, S. Cheng, C. Cometto, E. Anxolabéhère-Mallart, S-M. Ng, C-C. Ko, G. Liu, L. Chen, M. Robert, T-C. Lau, J. Am. Chem. Soc., 2016, 138, 9413–9416. [4] H. Rao, L. Schmidt, J. Bonin, M. Robert, Nature, 2017, 548, 74-77. [5] M. Wang, L. Chen, T-C. Lau, M. Robert, Angew. Chem. Int. Ed., 2018, 57, 7769-7773. [6] C. Cometto, R. Kuriki, L. Chen, K. Maeda, T-C. Lau, O. Ishitani, M. Robert, J. Am. Chem. Soc., 2018, 140, 7437-7440.

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P4. Catalysis Engineering for Sustainable Technologies J. Pérez-Ramírez

Institute for Chemical and Bioengineering, ETH Zurich, Switzerland, jpr@chem.ethz.ch.

Heterogeneous catalysis is quite possibly the most relevant discipline in the chemical industry, spearheading improvements in process sustainability by improving the exploitation of raw materials, enabling the transition from fossil to renewable feedstocks, reducing energy consumption, and minimizing the environmental footprint. To confront these challenges head on, this vibrant discipline is becoming increasingly design-driven, a shift which is facilitated by the availability of increasingly powerful tools that enable the continued development of fundamental knowledge over different time and length scales. The design of a heterogeneous catalyst, a dream not long ago, is becoming a reality. In this talk, I will discuss recent examples from my laboratory [1-15] to illustrate how this intellectual growth in the understanding of catalyzed processes can kindle revolutionary technological advancements. References [1] S. Mitchell, N.-L. Michels, K. Kunze, J. Pérez-Ramírez, Nat. Chem. 2012, 4, 825-831. [2] M. Milina, S. Mitchell, P. Crivelli, D. Cooke, J. Pérez-Ramírez, Nat. Commun. 2014, 5:3922. [3] V. Paunović, G. Zichittella, M. Moser, A.P. Amrute, J. Pérez-Ramírez, Nat. Chem. 2016, 8, 803-809. [4] M. Milina, S. Mitchell, D. Cooke, P. Crivelli, J. Pérez-Ramírez, Angew. Chem. Int. Ed. 2015, 54, 1591-1594 [5] O. Martin, A.J. Martín, C. Mondelli, S. Mitchell, T.F. Segawa, R. Hauert, C. Drouilly, D. Curulla-Ferré, J. Pérez-Ramírez, Angew. Chem. Int. Ed. 2016, 55, 6261-6265. [6] R. Lin, A.P. Amrute, J. Pérez-Ramírez, Chem. Rev. 2017, 117, 4185-4247. [7] G. Zichittella, N. Aellen, V. Paunović, A.P. Amrute, J. Pérez-Ramírez, Angew. Chem. Int. Ed. 2017, 56, 13670-13674. [8] V. Paunović, R. Lin, M. Scharfe, A.P. Amrute, S. Mitchell, R. Hauert, J. Pérez-Ramírez, Angew. Chem. Int. Ed. 2017, 56, 9791-9795. [9] D. Albani, M. Capdevila-Cortada, G. Vilé, S. Mitchell, O. Martin, N. López, J. Pérez-Ramírez, Angew. Chem. Int. Ed. 2017, 56, 10755-10760. [10] G.M. Lari, G. Pastore, M. Haus, Y. Ding, S. Papadokonstantakis, C. Mondelli, J. Pérez-Ramírez Energy Environ. Sci. 2018, 11, 1012-1029. [11] V. Paunović, P. Hemberger, A. Bodi, N. López, J. Pérez-Ramírez, Nat. Catal. 2018, 1, 363-370. [12] G.O. Larrazábal, T. Shinagawa, A.J. Martín, J. Pérez-Ramírez, Nat. Commun. 2018, 9:1477. [13] D. Albani, M. Shahrokhi, Z. Chen, S. Mitchell, R. Hauert, N. López, J. Pérez-Ramírez, Nat. Commun. 2018, 9:2634. [14] Z. Chen, E. Vorobyeva, S. Mitchell, E. Fako, M.A. Ortuño, N. López, S.M. Collins, P.A. Midgley, S. Richard, G. Vilé, J. Pérez-Ramírez, Nat. Nanotechnol. 2018, 13, 702-707. [15] S. Mitchell, E. Vorobyeva, J. Pérez-Ramírez, Angew. Chem. Int. Ed. 2018, doi:10.1002/anie.201806936.

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P5. Tuning the properties of cobalt nanoparticles for Fischer-Tropsch synthesis

Agustín Martínez

Instituto de Tecnología Química, Universitat Politècnica de València – Agencia Estaal Consejo Superior de Investigaciones Científicas (UPV-CSIC), Avda. de los Naranjos s/n, 46022 Valencia, Spain; Email: amart@itq.upv.es.

Supported cobalt catalysts are widely applied in Fischer-Tropsch synthesis (FTS) processes for the production of clean fuels from oil-alternative carbon sources such as coal, natural gas, and biomass via syngas (CO + H2). The active sites for CO and H2 activation, formation of CHx monomers, and C-C chain growth in Co-based FTS catalysts are metallic Co atoms (Co0) exposed on the surface of the supported cobalt nanoparticles (NPs). The electronic structure of the active Co0 sites, and hence their ability to activate CO (and H2) and to promote C-C coupling in the growing hydrocarbon chains depends, however, on different factors such as the specific location of the Co0 atoms in the nanoparticles (e.g. in flat surfaces or in defects), the extent of interaction of the metal NPs with the support surface, and the formation of alloys with other metals (e.g. with noble metal promoters), among others [1-5]. Therefore, tuning the properties of the Co0 NPs becomes essential to optimize their activity, selectivity, and stability in FTS. In this lecture, the most relevant approaches employed to tune the properties of the Co0 NPs during the preparation and activation of supported cobalt catalysts and their impact on the catalytic performance for FTS will be discussed. More specifically, the following aspects will be addressed: 1) the fine control of the metal particle size and size distribution by using advanced synthetic methods (e.g. micoemulsions) as alternative to conventional impregnation, 2) the role of the crystalline cobalt phase (i.e. fcc- versus hcp-Co0), 3) the control of metal-support interactions through varying the chemical identity of the support material and/or activation treatments, 4) the promotion of Co with noble metals (e.g. Ru, Re, Pt) and formation of bimetallic nanoparticles, and 5) the confinement of Co0 NPs in the inner space of ordered nanoporous materials. Moreover, the applications of advanced in situ characterizaton techniques revealing the dynamic behavior of Co0 NPs under FTS conditions will also be highlighted in selected examples. References [1] E. Iglesia, Appl. Catal. A: Gen., 1997, 161, 59-78. [2] A.Y. Khodakov, Catal. Today, 2009, 144, 251-257. [3] G.L. Bezemer, J.H. Bitter, H.P. C. E. Kuipers, H. Oosterbeek, J.E. Holewijn, X. Xu, F. Kapteijn, A.J. van Dillen, K.P. de Jong, J. Am. Chem. Soc., 2006, 128, 3956-3964. [4] G. Prieto, M.I.S. De Mello, P. Concepción, R. Murciano, S.B.C. Pergher, A. Martínez, ACS Catal., 2015, 5, 3323-3335. [5] C.J. Weststrate, J. van de Loosdrecht, J.W. Niemantsverdriet, J. Catal., 2016, 342, 1-16.

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ORAL COMMUNICATIONS

14

O1. Boomerang Activation in Heck-Mizoroki Reactions Catalyzed by Bis(N-Heterocyclic Carbene)palladium Complexes

A. M. Prieto, A. Ortiz, J. C. Flores, E. de Jesús Dpto. de Química Orgánica e Inorgánica, Instituto de Investigación Química "Andrés M. del Río", Universidad de

Alcalá, Campus Universitario, 28871 Alcalá de Henares, ernesto.dejesus@uah.es

For being attractive for industry, Pd loadings used in Heck-Mizoroki (HM) and other C-C coupling reactions should be reduced from the typical mol% range to the ppm or ppb level.[1] Herrmann et al. found 20 years ago that HM reactions were catalyzed by low loadings of N-heterocyclic carbene Pd(II) complexes (Pd NHCs).[2] The utility of NHCs was later brought into question by the development of HM reactions using very low amounts of ligand-free Pd salts.[3] The stability of the M-NHC bond might still help to recycle and reuse NHC catalysts, increasing their productivity. Accordingly, we decreased Pd use to 5 ppm thanks to the recovery of molecular weight-enlarged catalysts using nanofiltration membranes (Fig. 1a). We report here that the high recoverability was based in a boomerang initiation mechanism: at the start of the reaction, the excess of base promotes the slow delivery of ligand-free Pd species which are the true active catalyst (Fig. 1b); at the end of the reaction, ligand-free Pd is trapped again by the NHC ligand avoiding their degradation in the form of Pd black.

Figure 1. (a) Molecular-weight enlarged bis-NHC Pd catalysts. (b) Boomerang mechanism. References [1] D. Roy, Y. Uozumi, Adv. Synth. Catal, 2018, 306, 602. [2] W.A. Herrmann, M. Elison, J. Fischer, C. Köcher, G.R. Artus, Angew. Chem. Int. Ed. Engl., 1995, 34, 2371. [3] M. T. Reetz, J. G. de Vries, Chem. Commun., 2004, 1559. Acknowledgements We acknowledge Prof. A.G. Livinston and Dr. L. G. Peeva (Imperial College London) for their invaluable contribution to the nanofiltration experiments performed under continuous operation.

15

O2. Dehydrogenation reactions by design of well-defined supported catalysts

C. Mejuto, A. Mollar, D. Ventura-Espinosa, P. Borja, J. A. Mata Institute of Advanced Materials (INAM), Universitat Jaume I, Avda. Vicent Sos Baynat, s/n, 12071. jmata@uji.es

Homogeneous catalysts are superior to heterogeneous catalysts in terms of selectivity but their difficult separation from the products and subsequent reutilization is an important drawback that makes industries reluctant to use them in large-scale processes. Currently 90 % of industrial catalytic processes make use of heterogeneous catalysts. For these reasons, several efforts are being carried out for the immobilization of known and highly active homogeneous catalysts onto solid supports. In this regard, we have reported the immobilization of organometallic complexes onto graphene materials by -stacking interactions.1,2

Catalytic dehydrogenative reactions represent a suitable process to conduct organic transformations with the production of hydrogen as by-product. In the lasts years, some of these reactions have shown great potential as liquid organic hydrogen carriers (LOHC) for energy storage. In here, we present our last results in the hydrogen production by catalytic reactions and the evaluation as LOHCs.

References [1] Ventura-Espinosa, D.; Carretero-Cerdán, A.; Baya, M.; García,H.; Mata, J.A. Chem. Eur. J. 2017, 10815-10821. [2] Ventura-Espinosa, D.; Sabater, S.; Carretero-Cerdán, A.; Baya, M.; Mata, J.A. ACS Catal. 2018, 2558-2566. The authors thank the financial support from MINECO (CTQ2015-69153-C2-2-R), and Universitat Jaume I (P1.1B2015-09) and “Hyproxi” (VAL-2017-05). The authors are very grateful to the ‘Serveis Centrals d’Instrumentació Científica (SCIC)’ of the Universitat Jaume I.

16

O3. Palladium-mediated radical homo-coupling reactions: a surface catalytic insight

D. Pla, 1,* I. Favier,1 M.-L. Toro,1 M. Gómez1,*

17

O4. Mechanisms of Intramolecular Insertion in Copper Catalysed Carbene Transfers

M. Besora1 F. Maseras1,2 1 Institut Català D'Investigació Química (ICIQ), The Barcelona Institute of Science and Technology (BIST),

Avinguda Països Catalans 16, 43007 Tarragona, Catalonia, Spain .mbesora@iciq.cat 2 Universitat Autònoma de Barcelona, Edifici C, Facultat de Ciències, 08193 Cerdanyola del Vallès, Catalonia, Spain. Coinage metal catalysts are able to mediate the transfer of carbene units from diazo compounds to different types of nucleophiles. This reaction has been exploited to generate new value-added products. The group of Pedro Pérez has developed different catalysts with the tris(pyrazolyl)borate or N-heterocyclic carbene based ligands to functionalize a variety of organic compounds.1 In our group we have computationally investigated the reaction mechanisms for which a variety of such processes take place. Our investigations provide information on the nature of the intermediates, the different roles of the catalyst as well as the other species present in the reaction media.2 Recently, we have computationally studied the reactivity of copper catalysts with a very special type of diazocompounds: the diazoacetamides. The copper metallocarbene generated by the reaction of the diazoacetamide and the catalyst can undergo intramolecular insertion. Computationally the different reaction pathways that compete to give the different products and side reactions have been investigated.

NN2

HO

cat.N

O

+NO

R+

CONR

R2NOCR

R R

R R

Competitive products of the reaction of diazoacetamide mediated by coinage-metal catalysts.

References [1] A. Caballero, P.J. Pérez, Chem. Soc. Rev. 2013, 42, 8809. M. Besora, A.A.C. Braga, W.M.C. Sameera, J. Urbano, M.R. Fructos, P.J. Pérez, F. Maseras, J. Organomet. Chem. 2015, 784, 2. [2] M.R. Fructos, M. Besora, A.A.C. Braga, M.M. Díaz-Requejo, F. Maseras, P.J. Pérez, Organometallics 2017, 36, 172. M. Corro, M. Besora, C. Maya, E. Alvarez, J. Urbano, M.R. Fructos, F. Maseras, P.J. Perez, ACS Catalysis 2014, 4, 4215.

18

O5. N-Heterocyclic carbene complexes of first row transition metal complexes: synthesis, reactivity and applications C. Fliedel1, Lucas Thevenin1, Jean-Claude Daran1, R. Poli1

1 Laboratoire de Chimie de Coordination (LCC-CNRS), Université de Toulouse, CNRS, INPT, UPS, 205 route de Narbonne, 31077 Toulouse Cedex 4, France, e-mail: christophe.fliedel@lcc-toulouse.fr

Our group has been interested for a few years in organometallic-mediated radical polymerization (OMRP), a technique in which the control of the polymerization lies on the reversible equilibrium between an active radical species and a metal complex in its low oxidation state and a dormant organometallic species (Scheme, right) [1,2]. OMRP is a powerful tool for the polymerization of various monomers (M) [3].

The development of single-component OMRP initiators, i.e. metal complexes incorporating a metal-R bond (e.g. with R = alkyl group) that can be homolytically cleaved to generate radicals is of great interest to start radical polymerizations without the need of “classical” sensitive azo-initiators, and/or for post-polymerization functionalization [4].

In this context, the use of N-heterocylcic carbene (NHC) as supporting ligands, to ensure stabilization of the organometallic species and favor the lability of the R group as radical was studied. We will present here the synthesis and characterization of NHC-Mt and NHC-Mt-R (Mt = transition metal, R = alkyl, alkoxide) complexes, the study of the Mt-R bond reactivity and the use of the complexes as OMRP initiators.

Scheme. Example of NHC-Mt-R (R = alky, alkoxide…) metal complex and use as initiator for radical polymerization (left), and OMRP equilibrium (right). References [1] R. Poli, Angew. Chem. Int. Ed., 2006, 45, 5058-5070. [2] R. Poli, Chem. Eur. J., 2015, 21, 6988-7001. [3] S. Banerjee, V. Ladmiral, A. Debuigne, C. Detrembleur, R. Poli, B.M. Ameduri, Angew. Chem. Int. Ed., 2018, 57, 2934-2937. [4] J. Demarteau, A. Kermagoret, I. German, D. Cordella, K. Robeyns, J. De Winter, P. Gerbaux, C. Jérôme, A. Debuigne, C. Detrembleur, Chem. Commun., 2015, 51, 14334-14337.

19

O6. Novel approach for the synthesis of chiral tertiary α-aryl oxindoles via Pd-catalyzed decarboxylative protonation. An experimental and

theoretical mechanistic investigation

M. Biosca,1 M. Magre,1 M. Jackson,2 P. Guiry,2 P.-O. Norrby,3 O. Pàmies,1 M. Diéguez1

1 Universitat Rovira i Virgili, Departament de Química Física i Inorgànica, C/Marcel·lí Domingo, 1, 43007 Tarragona, Spain. E-mail: maria.biosca@urv.cat

2 Centre for Synthesis and Chemical Biology, School of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland.

3 Early Product Development, Pharmaceutical Sciences, IMED Biotech Unit, AstraZeneca, Pepparedsleden 1, SE-431 83 Mölndal, Sweden.

The enantioselective formation of C-C bond between an aryl group and a carbon α- to a carbonyl group is one of most challenging problems in organic chemistry.[1] In the last decade, the asymmetric α-arylation has attracted considerable attention due to α-aryl-carbonyl-containing molecules are present in a wide range of naturally occurring and biologically active compounds. Among them, compounds with oxindole core are very important because of this structural motif can be found in many natural products which exhibit an extensive range of biological properties. Great efforts have been made to prepare enantioselective α-substituted oxindoles. While catalytic synthesis of quaternary α-aryl oxindoles have been successfully achieved,[2] the synthesis of the corresponding tertirary α-aryl carbonyl containing compounds remains a challenge due to the ease at which such compunds racemize.[3] In this context, in this communication we will present the first catalytic asymmetric synthesis of chiral tertiary α-aryl oxindoles by Pd-catalyzed decarboxylative protonation of α-aryl-β-keto allyl esters, including experimental investigation of the reaction mechanism and theoretical studies to understand the nature of the enantioselective-determining step.

References [1] See, for example: a) J.F. Hartwig, Pure Appl. Chem. 2009, 71, 1417-1423; b) S. T. S. Sivanandan, A. Shaji, I. Ibanusaun, C.C.C. Johansson, T. J. Colacot, Eur. J. Org. Chem. 2015, 1, 38-49. [2] See, for instance; a) S. Lee, J.F. Hartwig, J. Org. Chem. 2001, 66, 3402-3415; b) A.B. Dounay, K. Hatanaka, J.K. Kodanko, M. Ostereich, L.E. Overman, L.A. Pfeifer, M.W. Weiss, J. Am. Chem. Soc. 2003, 125, 6261-6271. [3] a) M.J. Durbin, M.C. Willis, Org. Lett. 2008, 10, 1413-1415; b) R.A. Altman, A.M. Hyde, X. Huang, S.L. Buchwald, J. Am. Chem. Soc. 2008, 130, 9613-9620; c) P. Li, S.L. Buchwald, Angew. Chem. Int. Ed. 2011, 123, 6520-6524. Acknowledgements We gratefully acknowledge financial support from the Spanish Ministry of Economy and Competitiveness (CTQ2016-74878-P), European Regional Development Fund (AEI/FEDER, UE), the Catalan Government (2017SGR1472), and the ICREA Foundation (ICREA Academia award to M.D). M. M. thanks MINECO for a fellowship.

20

O7. Straightforward synthesis of hybrid nanoparticles stabilized by organophosphorous ruthenium dyes

E. Martín Morales, Y. Coppel, C. Bijani, V. Collière, P. Sutra, A. Igau, K. Philippot Laboratoire de Chimie de Coordination, LCC-CNRS, Université de Toulouse, CNRS, UPS, Toulouse, France

elena.martin@lcc-toulouse.fr Taking advantage of solar energy to make chemical processes more efficient and sustainable is among the most demanding challenges of our century. As the development of a single material photoactive in the visible region and capable of initiating a catalytic process is a complicated task, the combination of a photosensitive entity (organic or inorganic dye) with a metal entity (metal complex or nanoparticle as catalyst) becomes an alternative to photocatalyze chemical transformations. Due to their remarkable chemical stability and appropriate photophysical properties, Ru(II) polypyridyl complexes are commonly used as organometallic dyes. The singularity of our work is the incorporation of organophosphorous ligands in the coordination sphere of such Ru(II) polypyridyl complexes in order to tune their electrochemical and photophysical properties. [1,2] Regarding the synthesis of the metal nanoparticles, the organometallic approach is followed. [3] Under mild conditions, small ruthenium nanoparticles were, RuNPs, were prepared using organophosphorous Ru(II) polypyridyl complexes, [Ru], as stabilizers.

These new hybrid nanomaterials, [Ru]@RuNPs, have been characterized by XPS, IR, HR-TEM, liquid and solid-state NMR techniques. The results evidenced the interaction of the [Ru] complexes with the RuNPs surface. References [1] E. Lebon, R. Sylvain, R. E. Piau, C. Lanthony, J. Pilmé, P. Sutra, M. Boggio-Pasqua, J-L. Heully, F. Alary, A. Juris, A. Igau, Inorg. Chem. 2014, 53, 1946−1948. [2] P. Sutra, A. Igau, Coord. Chem. Rev. 2016, 308, 97-116. [3] C. Amiens, D. Ciuculescu-Pradines, K. Philippot, Coord. Chem. Rev. 2016, 308, 409-432.

21

O8. Magnetically recoverable photocatalysts based on metal oxide nanostructures

L. González1, M. E. Rabanal2, G. Salas1 1 IMDEA Nanociencia, Campus Universitario de Cantoblanco, 28049 Madrid, Spain., gorka.salas@imdea.org. 2 Universidad Carlos III de Madrid and IAAB, Dept. of Materials Science and Engineering and Chemical

Engineering, Avda. Universidad 30, 28911 Leganés, Madrid, Spain.

The use of heterogeneous photocatalysts for water remediation has been widely studied during the last decades [1]. In this work, the synthesis of γ-Fe2O3-ZnO hybrid nanostructures has been carried out with the aim of developing reusable photocatalysts that can be used in water dispersion (Figure 1). ZnO is a well known semiconductor photocatalyst, and maghemite (γ-Fe2O3) is superparamagnetic at the nanoscale. The degradation of methylene blue (MB) dye under UV irradiation has been chosen as a model reaction.

Figure 1. Scheme illustrating the magnetic recovery of the hybrid nanostructures after photocatalysis.

Results show that the γ-Fe2O3-ZnO hybrid nanostructures exhibit superior performance to that of the ZnO or γ-Fe2O3 alone. In addition, their reuse in MB degradation after magnetic recovery showed that the catalytic properties are preserved after at least three cycles. In summary, γ-Fe2O3-ZnO hybrid nanostructures are a suitable candidate for its use in environmental applications to solve specific problems related to the removal of organic contaminants from water. References [1] M. A. Fox, M. T. Dulay, Chem. Rev., 1993, 93, 341-350; E. L. Cates, Environ. Sci. Technol. 2017, 51, 757−758.

22

O9. Controlled Synthesis of Ru Nanoparticles Covalent Assemblies Y. Min1, I. C. Gerber 2, H. Nasrallah3, D. Poinsot3, J. C. Hierso3,4, M. R. Axet1*, P.

Serp1* 1 Laboratoire de Chimie de Coordination UPR CNRS 8241, composante ENSIACET, Universite de Toulouse UPS-

INP-LCC, 4 allee Emile Monso BP 44362, 31030 Toulouse Cedex 4 (France)]. e-mail: yuanyuan.min@lcc-toulouse.fr.

2 Université de Toulouse, INSA, UPS, CNRS, LPCNO (IRSAMC), F-31077 Toulouse, France. 3 Institut de Chimie Moléculaire de l'Université de Bourgogne (ICMUB), UMR-CNRS 6302, Université de

Bourgogne Franche-Comté (UBFC), Dijon, France. 4 Institut Universitaire de France (IUF).

Organized networks of metal nanoparticles (NPs) are attractive because of an atomically defined environment and because different arrays of the same metal nanoparticles may display different properties. However, the development of highly anisotropic assemblies is still challenging. We have already reported the synthesis of Ru NPs assemblies stabilized by functionalized fullerene [C66(COOH)12], with a control of interparticle distance by covalent bonds [1]. Here, several functionalized adamantanes [2] bearing two functional groups have been used as building blocks to construct innovative networks of NPs. Both carboxylic and amine adamantane and diadamantane derivatives were selected as ligands to stabilize new nanostructures. The shape and size of Ru NPs was controlled by the nature of the functional group of the ligand and by tuning the Ru/ligand ratio. SAXS analyses of the samples of Ru/Ad(COOH)2 with different Ru/ligand ratio (5/1, 10/1 and 20/1) show that in these materials the Ru NPs are ordered with Ru NPs distances around 2.5-2.7 nm (Figure 1). The as-obtained materials have been further characterized by a large variety of techniques including HREM, STEM-HAADF and WAXS. The interaction between Ru NPs and the stabilizers was investigated through isotopically labeled ligands, using ATR-IR and SSNMR techniques. As a support, Density Functional Theory (DFT) calculations have been performed to establish atomistic simulation of this innovative nanostructures. These nanostructures have been tested as catalysts in several hydrogenation reactions. References [1] Leng, F.; Gerber, I. C.; Lecante, P.; et al. Chem. Eur. J. 2017. 23(54), 13379. [2] Gunawan, M. ; Moncea, O. ; Poinsot, D. et al. Adv. Funct. Mater. 2018. DOI: 10.1002/adfm.201705786.

a

0.01 0.10.1

1

10

100

1000

10000

I(q)

q(A-1)

Ru/Ad(COOH)2 20/1Ru/Ad(COOH)2 10/1Ru/Ad(COOH)2 5/1

b

23

O10. Selective Hydrogenation of Alkynes into (Z)-alkenes with Nickel Nanoparticles Stabilized by Imidazolium-aminidate Ligands

A. M. López-Vinasco,1 L. M. Martínez-Prieto,1,2 J. M. Asensio,1 B. Chaudret,1 J. Cámpora,3 P. W. N. M. van Leeuwen1

1 LPCNO; Laboratoire de Physique et Chimie des Nano-Objets, UMR5215 INSA-CNRS-UPS, Institut des Sciences Appliquées, 135, Avenue de Rangueil, F-31077 Toulouse, France.

2 Instituto de Tecnología Química, CSIC-Universitat Politécnica de València. Avda. Los Naranjos S/N, 42006 Valencia, Spain.

3 Instituto de Investigaciones Químicas, CSIC-Universidad de Sevilla. C/ Américo Vespucio, 49, 41092 Sevilla, Spain.

The selective hydrogenation of alkynes into (E)-or (Z)-alkenes is an important synthetic tool in fine chemistry and petrochemical and polymerization industries.[1] Until now, classical heterogeneous catalysts used in this reaction are based on noble metals,[2] the Pd catalysts being those that have predominated in this transformation. However, the selective conversion of alkynes into alkenes requires the use of a Pd catalyst partially poisoned with lead (Lindlar catalysts),[3] leading to harmful wastes and heavy metal residues in the products. Therefore, new approaches employing environmentally friendly, low-cost, chemoselective and recyclable catalysts are desirable. In this context, Ni nanoparticles have been applied recently in the selective hydrogenation of alkynes,[4] showing high selectivities towards the corresponding (Z)-alkenes. Herein we report a series of new Ni NPs stabilized by three different imidazolium-amidinate ligands (L1=ICy•(p-tol)NCN, L2=ICy•(p-anysil)NCN and L3=ICy•(p-ClC6H4)NCN), which were fully characterized by different techniques (TEM, HRTEM, WAXS, XRD, AAS, VSM and XPS). These new nanocatalysts present a remarkable selectivity in the semi-hydrogenation of 3-hexyne into (Z)-3-hexene under very mild reaction conditions (room temperature and 1 bar H2). Interesting differences were observed in terms of activity by modifying the electron donor/acceptor (-Cl, Me, -OMe) groups in the N substituents of the amidinate moiety. Recycling experiments were successfully performed and the catalysts were easily recovered and reused 3 times. References [1] a) C. Oger, L. Balas, T. Durand, J. M. Galano, Chem. Rev. 2012, 113, 1313-1350. b) P. Kittisakmontree, B. Pongthawornsakun, H. Yoshida, S.-i. Fujita, M. Arai, J. Panpranot, J. Catal. 2013, 297, 155-164. [2] J. A. Delgado, O. Benkirane, C. Claver, D. Curulla-Ferré, C. Godard, Dalton Trans., 2017, 46, 12381-12403. [3] J. L. Fiorio, N. López, L. M. Rossi, ACS Catal., 2017, 7, 2973−2980 [4] a) M. Díaz de los Bernardos, S. Pérez-Rodríguez, A. Gual, C. Claver, C. Godard, Chem. Commun., 2017,53, 7894-7897. b) X. Wen, X. Shi, X. Qiao, Z. Wu, G. Bai, Chem. Commun., 2017, 53, 5372—5375. c) H. Konnerth, M. H. G. Prechtl, Chem. Commun., 2016, 52, 9129-9132.

24

O11. Synthesis of chiral γ-aminobutyric esters via Rhodium catalysed asymmetric hydroaminomethylation of α-alkyl acrylates

A. Cunillera1, C. Godard1, A. Ruiz1

1 Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, C/Marcel·lí Domingo s/n, 43007, Tarragona, Spain

anton.cunillera@urv.cat

Amines constitute powerful building blocks in the synthesis of biological active molecules and agrochemicals, therefore the efficient and selective synthesis of chiral amines using easily available and abundant precursors is a long-standing goal of chemical research.[1] In this context, rhodium catalyzed hydroaminomethylation is an attractive reaction, since it allows the direct synthesis of amines starting from readily available alkenes in a high atom economy process.[2] Among the different amine containing molecules, γ-aminobutyric acids (GABA) and derivatives have attracted considerable attention since they play an important role in reducing neuronal excitability and this scaffold is present in several natural products.3 For this reason, the rhodium catalyzed asymmetric hydromainomethylation of acrylates is a promising strategy for the direct synthesis of GABA.[3] In this work, we report the synthesis of chiral γ-aminobutyric esters via rhodium catalyzed asymmetric hydroaminomethylation of α-alkyl acrylates in the presence of different amines. Optimization of the conditions and screening of phosphorus ligands were tested in order to control the regio- and chemoselectivity of the process. Moreover, the control in the regioselectivity did not only allow to obtain the desired γ-aminobutyric ester, but also to produce β-amino ester depending on the ligand and conditions applied.

[1] J. W. Blunt, B. R. Copp, R. A. Keyzers, M. H. G. Munro, M. R. Prinsep, Nat. Prod. Rep. 2012, 29, 144.

[2] a) D. Crozet, M. Urrutigoïty, P. Kalck, Chem. Cat. Chem. 2011, 3, 1102. b) C. Delphine, C. E. Kefalidis, M.

Urritigoïty, L. Maron, P. Kalck, ACS Catal. 2014, 4, 435. c) C. Chen, X.-Q. Dong, X. Zhang, Org. Chem. Front. 2016,

3, 1359. d) P. Kalck, M. Urrutigoïty, Chem. Rev. 2018, 118, 3833.

[3] J. H. Chung, L. Hunter, J. Org. Chem, 2011, 76, 5502.

25

O12. Synthesis of new bis(boryl)acetal compounds from CO2 D. Zhang1 , S. Bontemps1

1 LCC CNRS, 205 Route de Narbonne, 31077 Toulouse Cedex 4, dan.zhang@lcc-toulouse.fr.

As a nontoxic and sustainable carbon source, carbon dioxide has attracted increasing attention over the last few decades. Significant efforts have been devoted to the transformation of CO2 and especially its reduction under mild conditions. However the selective reduction of CO2 to the formaldehyde level is still a challenge.[1] The use of hydroborane allowed selective CO2 reduction to bis(boryl)acetal (BBA) under mild conditions (Figure 1).[2] Unfortunately, questions remain on this selectivity and very few examples of bis(boryl)acetals are reported. We recently discovered that the boryl moiety has a big impact on the reactivity of BBA.[3] We thus aimed at synthesizing new bis(boryl)acetal compounds. I will present our last results on the use of non-commercially available hydroboranes and the variation of the catalyst based on 1st row metal hydride complexes (M= Fe, Co, Mn).

Figure 1. CO2 hydroboration

References [1] S. Bontemps, L. Vendier, S. Sabo-Etienne, J. Am. Chem. Soc., 2014, 136, 4419-4425. [2] G.Jin, C. G. Werncke, S. Bontemps, J. Am. Chem. Soc., 2015, 137, 9563-9566. [3] submitted for publication.

26

O13. Remote C-H Oxidation guided by Supramolecular Recognition G. Olivo,1 G. Farinelli,2 A. Barbieri,2 O. Lanzalunga,2 S. Di Stefano 2, M. Costas1

1QBIS-CAT, IQCC, Universitat de Girona, C/ Pic de Peguera 15, 17003, Girona, Spain, giorgio.olivo@udg.edu 2 Università di Roma La Sapienza, Piazzale Aldo Moro 5, 00182, Rome, Italy

Selectivity is a longstanding challenge in aliphatic C-H bond functionalization, given the ubiquity of such bonds in organic compounds. State-of-the-art strategies for selective functionalization rely either on the higher reactivity of certain sites (due to electronic or steric factors) or on a coordinating group to direct the reaction on a nearby site. However, C-H bonds that do not meet these requirements are very difficult to target. Bioinspired Fe and Mn C-H hydroxylations with H2O2 [1] are no exception in this regard, as the most electron-rich and sterically accessible CH bonds are the preferred oxidation sites. Seeking to overcome these limitations, we designed and implemented a supramolecular strategy to target remote C-H bonds. We decorated a Mn catalyst with an 18-crown-6 ether receptor that can recognize protonated primary amines.[2] Such binding places C8 and C9 C-H bonds of the substrate in the range of the oxidizing species, thus enabling a geometrical control of the oxidation selectivity (Figure 1). Herein, the application of this strategy to the remote, selective oxidation of linear amines and more elaborated substrates will be presented.

Figure 1 Supramolecular control of C-H oxidation selectivity

References [1] W. N. Oloo, L. Que, Jr Acc. Chem. Res. 2015, 48, 2612; M. S. Chen, M. C. White, Science 2007, 318, 783-787. [2] G. Olivo, G. Farinelli, A. Barbieri, O. Lanzalunga, S. Di Stefano, M. Costas, Angew. Chem. Int. Ed. 2017, 56, 16347.

27

O14. Visible light metallaphotoredox strategies towards the cleavage of Csp3-Cl bonds

Miguel Claros1, Jordi Aragón-Artigas1, Felix Ungeheuer1, Alicia Casitas,2* Julio Lloret-Fillol1,3*

1 Institut Català d’Investigació Química (ICIQ), The Barcelona Institute of Science and Technology (BIST), Av. Països Catalans 16, E-43006, Tarragona (Catalonia, Spain). 2 Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus Montilivi, E-17003, Girona (Catalonia, Spain). E-mail: alicia.casitas@udg.edu 3 Catalan Institution for Research and Advanced Studies (ICREA), Passeig Lluïs Companys, 23, 08010, Barcelona (Catalonia, Spain). E-mail: jlloret@iciq.es

Recent visible light metallaphotoredox methodologies have allowed the construction of

a large variety of C-C and C-heteroatom bonds.[1] Most of these novel photocatalytic protocols are limited to highly active aryl and alkyl iodides and bromides as coupling partners.[2] Although alkyl chlorides are available, economic and bench-stable feedstocks, the chemical inertness of Csp3-Cl bonds hampers their use as electrophilic partners in most of catalytic methodologies, as showcased by the narrow number of transition metal-catalyzed reactions towards this endeavor.[3]

Herein we present an earth-abundant metal-based metallaphotoredox catalytic system (Cu, Co/Ni) that enables the functionalization of Csp3-Cl bonds under visible light irradiation and mild conditions. The in situ photoreduction of cobalt or nickel complexes bearing penta- or tetracoordinate nitrogen-based ligands is a key design element to enable the activation of unactivated Csp3-Cl bonds. This approach unveils a sustainable synthetic protocol towards the construction of carbocycles via intramolecular reductive cyclization of alkyl chlorides that bear tethered alkenes with broad functional group tolerance.[4]

References [1] J. Twilton, C. Le, P. Zhang, M. H. Shaw, R. W. Evans, D. W. C. MacMillan Nature Reviews 2017, 1, 0052. [2] a) H. Kim, C. Lee Angew. Chem. Int. Ed. 2012, 51, 12303. b) G. Revol, T. McCallum, M. Morin, F. Gagosz, L. Barriault Angew. Chem. Int. Ed. 2013, 52, 13342. c) C. P. Johnston, R. T. Smith, S. Allmendinger, D. W. C. MacMillan Nature 2016, 536, 322. [3] a) O. Vechorkin, D. Barmaz, V. Proust, X. Hu J. Am. Chem. Soc. 2009, 131, 12078. b) M. Börjesson, T. Moragas, R. Martin, J. Am. Chem. Soc. 2016, 138, 7504. [4] M. Claros, F. Ungeheuer, A. Casitas, J. Lloret-Fillol manuscript in preparation.

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O15. Co3O4 nanoparticle-based dyads for light-driven water oxidation J. De Tovar1, N. Romero1, S. Denisov2, R. Bofill1, C. Gimbert-Suriñach3, D.

Ciuculescu-Pradines4, S. Drouet4, A. Llobet1,3, P. Lecante5, V. Colliere4, Z. Freixa6, N. McClenaghan2, C. Amiens4, J. García-Antón1, K. Philippot4, and X. Sala1

1 Departament de Química, Facultat de Ciències, Universitat Autònoma de Barcelona, 08193 Bellaterra, Catalonia (Spain). Nuria.Romero@uab.es

2 Institut des Sciences Moléculaires, Université Bordeaux, 351 Cours de la Libération, 33405 Talence (France) 3 Institut Català d’Investigació Química (ICIQ), Av. Països Catalans 16, 43007 Tarragona, Catalonia (Spain) 4 LCC-CNRS, Université de Toulouse, CNRS, UPS, 205, route de Narbonne, F-31077 Toulouse (France) 5 CNRS, CEMES, 29 rue J. Marvig,31055 Toulouse (France) 6Department of Applied Chemistry, (UPV-EHU), 20080 San Sebastián (Spain) & IKERBASQUE, Bilbao (Spain)

The replacement of fossil fuels by a clean and renewable energy source is one of the most urgent and challenging issues in our society. A particularly attractive solution is the production of hidrogen from water splitting (WS) by sunlight as driving force.[1] Therefore, an enormous effort is needed for the development of efficient catalysts to speed up the water oxydation (WO) half reaction, which is the bottleneck step. Several examples of coordination complexes, in situ-formed oxides and colloidal species have been described acting as rugged, low-overpotential water oxidation catalysts (WOCs).[2] However, the factors controlling their efficiency are still not rationally understood. In this work, Co nanoparticles (NPs) have been prepared by hydrogenation of the organometallic complex [Co(3-C8H13)(4-C8H12)] in 1-heptanol and then transformed into Co3O4 NPs using mild oxidative reaction conditions. The covalent grafting of photosensitive polypyridyl-based RuII complexes onto the surface of Co3O4 NPs afforded hybrid nanostructured materials able to photo-oxidize water into O2. Hybrid nanocatalysts display better catalytic performance than simple mixtures of non-grafted photosensitizers and Co3O4 NPs, thus evidencing the advantage of the direct coupling between the two entities.

References [1]. S. Berardi, S. Drouet, L. Francàs, C. Gimbert-Suriñach, M. Guttentag, C. Richmond, T. Stolla, A. Llobet, Chem. Soc. Rev. 2014, 43, 7501; Nocera, Acc. Chem. Res. 2017, 50, 616. N.S. Lewis, Science, 2016, 351, aad19201. [2]. R. Matheu, L. Francàs, P. Chernev, M. Z. Ertem, V. Batista, M. Haumann, X. Sala and A. Llobet, ACS Catal. 2015, 5, 3422; P. Garrido-Barros, C. Gimbert-Suriñach, R. Matheu, X. Sala and A. Llobet, Chem. Soc. Rev., 2017, 46, 6088-6098.

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O16. Synthesis of pharmacologically relevant cyclobutanes by regio- and stereoselective [2+2]-photocycloadditons

S. Sierra,1 J. M. Mateo,2 M. V. Gómez,2 C. Cativiela,1 E. Gómez Bengoa,3 E. P. Urriolabeitia1

1 ISQCH (CSIC - Universidad de Zaragoza), Pedro Cerbuna 12, 50009 Zaragoza, Spain; esteban@unizar.es 2 IRICA, Universidad de Castilla La Mancha, Avda Camilo José Cela s/n, 13071 Ciudad Real, Spain 3 Dpto. Química Orgánica I, Universidad del País Vasco, UPV-EHU, 20080 Donostia − San Sebastián, Spain

In this communication we present the regio- and stereoselective synthesis of 1,3-diaminotruxillic and 1,2-diaminotruxinic acid derivatives from [2+2]-photodimerization of (Z)-4-aryliden-2-(alkyl,aryl)-5(4H)-oxazolones. Truxillic acids are of outstanding interest due to their pharmacological properties. Under direct irradiation conditions 1,3-diaminotruxillic acids are selectively obtained by 1,3-coupling (head-to-tail) of Z-oxazolones.[1] However, when the irradiation is performed in the presence of a Ru-coordination complex, a complete change in the orientation of the reaction is observed, and 1,2-diaminotruxinic acids are obtained as single regio- and stereoisomers by head-to-head 1,2-coupling of E-oxazolones. In fact, from six possible diastereoisomers only one of them is finally isolated. The reaction is highly sensitive to the temperature, and additional isomers or rearrangement processes of high synthetic interest can be detected.

The determination of the mechanism through DFT methods of this energy transfer-based photochemical processes provides a reasonable interpretation of the experimental facts. We have been able to fully determine the role of the ruthenium complex and the ultimate reason of the selectivity, which seems to reside in the different spin state (S1 vs T1) of the oxazolone in the excited state. References [1] A. García-Montero, A. M. Rodríguez, A. Juan, A. H. Velders, A. Denisi, G. Jiménez-Osés, E. Gómez-Bengoa, C. Cativiela, M. V. Gómez, E. P. Urriolabeitia, ACS Sustainable Chem. Eng. 2017, 5, 8370-8381

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O17. Selective Hydrogenation of Fatty Acids with Doped Graphene-Supported Ruthenium Nanoparticles

L. M. Martínez-Prieto1, M. Puche,1 B. Chaudret2, A. Corma1. 1 ITQ, Instituto de Tecnología Química,Universitat Politècnica de València (UPV), Av. de los Naranjos S/N 46022,

Valencia, España. e-mail: luimarp5@upvnet.upv.es 2 LPCNO, Laboratoire de Physique et Chimie des Nano-Objets (INSA-CNRS) 135, Avenue de Rangueil, F-31077

Toulouse, France.

From an environmental point of view, the use of biomass and vegetable oils to generate high-value chemicals is fundamental for a more sustainable future. In particular, the hydrogenation of fatty acids to alcohols is of great interest for the pharmaceutical and fine-chemical industries.[1,2] The current industrial process employs Cu-Cr based catalysts under harsh conditions (250-350 ºC and 100-200 bar), and are subject of catalyst deactivation and poor selectivity (Scheme 1).[1] Therefore, a stable, selective and active catalyst that operates in mild conditions is highly required for the catalytic hydrogenation of fatty acids to alcohols.

Cu-Cr catalysts

fatty acid100-200 bar H2

250-350 ºC

OH

O

nOH

n

fatty alcohol

· Harsh conditions· Catalyst deactivation· Poor selectivity

Scheme 1. Industrial production of fatty alcohols from fatty acids.

Our strategy was to employ as catalyst doped graphene-supported ruthenium nanoparticles (Ru NPs) prepared by an organometallic approach (Scheme 2).[3] The nature of the graphene introduces interesting differences in terms of stabilization, NP dispersion, and catalytic reactivity. The obtained catalytic systems were applied to the hydrogenation of palmitic acid to cetyl alcohol, with interesting activities and selectivities under milder reaction conditions.

Scheme 2. Synthesis of Ru NPs supported in a N-doped graphene.

References [1] M. A. Sánchez, G. C. Torres, V. A. Mazzieri and C. L. Pieck, J. Chem. Tech. Biotech. 2017, 92, 27-42. [2] D. S. Thakur and A. Kundu, J. Am. Oil Chem. Soc. 2016, 93, 1575-1593.

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[3] L. M. Martínez-Prieto, B. Chaudret, Acc. Chem. Res. 2018, 51, 376-384. O18. Developing the Hydrogen Storage Technology: Highly Efficient

Dehydrogenation of Ammonia Boranes with Ru(II) Complexes Bearing 2-(2-Aminophenyl)-1H-benzimidazole

G. Espino1, M. Martínez-Alonso,1 M. Ruiz de Castañeda,1 A. D. Phillips2, Crystal O’Connor2 A. M. Rodríguez3

1 Dept. of Chemistry, University of Burgos, Pza. Misael Bañuelos s.n. 09001, Burgos, Spain, gespino@ubu.es. 2 School of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland. 3 Dept. of Inorganic and Organic Chemistry and Biochemistry, Univ. de Castilla-La Mancha, Av. Camilo J. Cela

10, 13071, Ciudad Real, Spain.

Ammonia Borane (AB) exhibits high potential as a H2 storage material due to its high H to weight ratio. The controlled dehydrogenation of AB offers reduced risk of both explosion and volatile dissipation. Moreover, the release of H2 from AB through homogeneous catalytic dehydrogenation is very advantageous since it guarantees high selectivity in terms of product formation.[1] In this communication, we present the rational design of two Ru(II) 6-arene complexes supported by the bidentate 2-(2-aminophenyl)-1H-benzimidazole ligand as catalysts for the dehydrogenation of amine boranes. Both derivatives are highly active in this catalytic process at moderate temperatures. Moreover, both complexes yield more than two equivalents of H2 per molecule of AB. Aside from a comprehensive 11B NMR investigation, a mechanism is proposed on the basis of experimental studies and theoretical calculations.

Figure 1. (a) Dehydrogenation of Amine-borane. (b) General Structure of the Ru(II) catalysts. [1]OTf,

X = Cl A = OTf, [2]I X = A = I. References [1] D. F. Schreiber, C. O´Connor, C. Grave, Y. Ortin, H. Müller-Bunz, A. D. Phillips, ACS Catal. 2012, 2, 2505-2511.

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33

O19. Iridium catalyzed functionalization of amines with CO2 and hydrosilanes

Francisco J. Fernández-Alvarez Departamento de Química Inorgánica – Instituto de Síntesis Química y Catálisis Homogénea (ISQCH).

Universidad de Zaragoza. Facultad de Ciencias 50009, Zaragoza – Spain; paco@unizar.es

The catalytic reaction of secondary and/or primary amines with CO2 and silicon-hydrides as reductants has emerged as a promising technology that allows the selective formylation and/or methylation of N-H bonds.[1] Moreover, some catalytic systems have promoted the selective formation of silylcarbamates or aminals.[1,2] The research team I lead has contributed in the development of this chemistry, particularly in the case of iridium-catalyzed processes.[3] This oral contribution summarizes our recent unpublished results showing the influence of the nature of the catalyst, the reductant and the reaction conditions on the performance and selectivity of the different catalytic processes that have been studied.

References [1] C. Chauvier, T. Cantat, ACS Catal. 2017, 7, 2107-2115. [2] F. J. Fernández-Alvarez, L. A. Oro, ChemCatChem 10.1002/cctc.201800699. [3] F. J. Fernández-Alvarez, R. Lalrempuia, Luis A. Oro, Coord. Chem. Rev. 2017, 350, 49-60.

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O20. Dry reforming of methane over hydroxyapatite supported nickel and cobalt catalysts

D. Pham Minh1, T. S. Phan1, Q. Tran Thi1,2, A. Nzihou1, H. Nguyen Xuan2, D. Grouset1

1 Université de Toulouse, IMT Mines Albi, UMR CNRS 5302, Centre RAPSODEE, Campus Jarlard, F-81013 Albi cedex 09, France, e-mail: doan.phamminh@mines-albi.fr. 2 Faculty of Chemistry, VNU University of Science, 19 Le Thanh Tong, Hoan Kiem, Hanoi, Viet Nam

Dry reforming of methane (DRM) consists on the transformation of an equimolar mixture of CH4 and CO2 to CO and H2. This reaction could be an alternative to steam reforming of methane and allows valorising CO2 to chemicals. From thermodynamic point of view, this reaction is only favored above 700°C and low pressure (i.e. atmospheric pressure). It is also accompanied with the formation of different by-products including solid carbon, water and traces of light hydrocarbons. DRM is highly favored by the use of a solid catalyst [1]. Nickel-based catalysts appear as the most promising and have been largely studied in the literature. However, the deactivation phenomenon is omnipresent under the experimental conditions of DRM reaction because of solid carbon deposition on catalyst surface and thermal sintering of catalyst at high temperature. Hydroxyapatite (Ca10(PO4)6(OH)2) – or HAP – has been recently investigated as catalyst support for DRM reaction and very promising results have been obtained [2]. By controlling the molar ratio of Ca to P, the acido-basicity of this support can be adjusted which is a crucial factor for CO2 adsorption and dissociation. This support is also well known by its high thermal stability as well as its good ionic exchange capacity for divalent metals such as nickel and cobalt. In this work, DRM reaction over HAP-based catalysts has been studied. HAP support was synthesized from calcium carbonate (CaCO3) or calcium nitrate (Ca(NO3)2) as calcium sources and ammonium dihydrogen phosphate (NH4H2PO4) as phosphate source. Different monometallic or bimetallic catalysts containing Ni and/or Co were prepared and evaluated in DRM reaction. Different physico-chemical characterizations were also carried out to link the catalytic performance with the properties of the prepared catalysts.

References [1] N. A. K. Aramouni, J. G. Touma, B. A. Tarboush, J. Zeaiter, M. N. Ahmad, Ren. Sust. Ener. Rev. 2018, 82, 2570-2585. [2] T. S. Phan, A. R. Sane, B. Rêgo De Vasconcelos, A. Nzihou, P. Sharrock, D. Grouset, D. Pham Minh, Appl. Catal. B: Env. 2018, 224, 310-321.

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O21. CO2 Methanation over Ni/SiRAlOx Catalyst using Magnetic Nanoparticles as a Magnetically-Induced Heating Source

J. M. Asensio,1 S. S. Kale,1 M. Estrader,1 J. Marbaix,1 A. Bordet,1,2 M. Werner,1 P. F. Fazzini,1 K. Soulantika,1 B. Chaudret.1

1 LPCNO, Université de Toulouse, CNRS, INSA, UPS, 135 avenue de Rangueil, 31077 Toulouse, France. 2 Currently at Max-Planck Institute for Chemical Energy Conversion, Stiftstraße 34-36, 45470 Mülheim an der

Ruhr.

The rapid development of modern society has led to an increase in global energy consumption. As a consequence, CO2 concentration in the atmosphere is continuously increasing, which is also a major component in greenhouse gas.[1] Thus, the reduction of CO2 levels in order to minimize its negative impact to the modern civilization has enforced to develop technologies which make an effective use of renewable energy sources. A possible way to utilize CO2 is the catalytic hydrogenation to produce methane and water. Traditionally, CO2 methanation is performed in a continuous flow reactor using conventional oven to heat the feed gases, which consumes a high amount of energy. In this context, magnetic hyperthermia is a topic of interest that presents promising applications in heterogeneous catalysis. Through this technique, magnetic nanoparticles (NPs) are directly transforming the energy of the magnetic field into heat, which allows heating the catalyst from within its structure. Recently, we have reported the synthesis of Fe2.2C NPs displaying far larger heating properties than any previously described material. [2]. A catalyst based on Ru and Fe2.2C NPs supported on SiRAlOx displayed very good activities in CO2 methanation using a magnetic field of 40 mT at a f of 300 kHz.. Nevertheless, in order to minimize the amplitude of the magnetic field during the catalytic reaction and to increase the energetic efficiency, Co seems to be a better candidate as heating source because it posseses a higher value of Curie Temperature TC (TC~1150 ºC). On the other hand, Ni is also an active catalyst for CO2 methanation and it constitutes a cheaper and more environmentally friendly alternative to Ru. Thus, in the present study we have synthesized a new catalytic system based on Ni and Fe2.2C NPs supported on SiRAlOx for CO2 methanation. We have also explored the viability of Co nano-rods (NRs) as a heating source in the reaction, which were activated after addition of small amounts of Fe2.2C NPs. This strategy allowed us to obtain >90% of CO2 conversion with very high selectivity towards the formation of CH4, using very low magnetic field amplitudes (16 mT). References [1] Younas, M.; Sohail, M.; Leong, L. K.; Bashir, M. J. K.; Sumathi, S. Int. J. Environ. Sci. Technol. 2016, 13, 1839 [2] Bordet, A.; Lacroix, L.-M.; Fazzini, P.-F.; Carrey, J.; Soulantica, K.; Chaudret, B. Angew. Chem., Int. Ed. 2016, 55, 15894

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O22. One-pot Butyl Levulinate Production from Fructose and Butanol over Dowex 50Wx2: Water Effect on Catalytic Activity

G. Freddi1, G. Gordillo2, E. Ramírez2, R. Bringué2, M. Iborra2, J. Tejero2, F. Cunill2 1 Department of Industrial Chemistry “Toso Montanari”, University of Bologna, Viale del Risorgimento 4, 40136,

Bologna, Italy. 2 Department of Chemical Engineering and Analytical Chemistry, University of Barcelona, Marti i Franqués 1-11,

08028, Barcelona, Spain, jtejero@ub.edu. Taking into account the depletion of fossil fuel resources and the degradation of environment quality mainly due to transport sector, European Union has been introduced several directives to improve fuel quality by increasing oxygenates content in fuels to 15% by 2020. Butyl levulinate (BL), a levulinic acid (LA) derivated-compound, is a second generation oxygenate that can be blend in commercial diesel because its good cold flow properties and its boiling point lies within the low part of the diesel distillation curve. BL is conventionally obtained by direct esterification of levulinic acid with butanol in the presence of acid catalysts [1]. Since pure LA is an expensive raw material, BL can be alternatively produced from carbohydrates obtained from lignocellulose hydrolysis on acid catalysis.

In this work, BL is produced from fructose (F) and butanol (BuOH) over 1 g of Dowex 5Wx2 (400 mesh), an acidic ion-exchange resin, at 120ºC and 20 MPa in a batch stirred tank reactor during 8 h. The initial homogeneous feed consisted of 70 mL of a BuOH-water mixture (water/BuOH molar ratio: 0.9) and 1.7 g of fructose (F/BuOH molar ratio:0.013). In the experiments, water/BuOH molar ratio was varied from 0.9 to 0 to assess catalytic activity.

Results show that F dehydrates readily to 5-hydroxymethylfurfural (HMF), which in the presence of water and BuOH forms butoxymethylfurfural (BMF) and it is rehydrated to LA, both BMF alcoholysis and LA esterification produce BL; formic acid (FA) and butyl formate (BF) being byproducts. In all the experiments, fructose conversion at 8 h was complete but the experiment with the highest water amount (99%). Considering the saccharides insolubility in alcohols, the amount of water in the experiments was tuned in terms of compounds selectivity: BL selectivity increased from 28 to 57 with the decrease in water/BuOH molar ratio although BL selectivity reached a plateau value at water/BuOH ratio values lower than 0.21. In a water-rich medium (water/BuOH molar ratio higher than 0.41), selectivity to HMF and BL diminished due to the polymerisation of F and HMF into humins [2]. References [1] M. A. Tejero et al., Appl. Catal. A – Gen., 2016, 51, 56-66. [2] X. Hu and Li, C.-Z., Green Chem., 2011, 13, 1676-1679.

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O23. Oxidation catalysis under green chemistry conditions Y. Wang1,2, P. Guillo1,2, D. Agustin1,2, J.-C. Daran1,3, E. Manoury1,3, R. Poli1,3

1 CNRS, Laboratoire de Chimie de Coordination, Toulouse, France 2 Université de Toulouse, Institut Universitaire de Technologie Paul Sabatier, Castres, France. 3 Université de Toulouse, UPS, INPT, Toulouse Cedex 4, France E-mail: yun.wang@lcc-toulouse.fr

Oxidation reactions play an important role in our daily lives. For example, epoxides

are key intermediates for many syntheses and are widely used in the chemical industry. Access to this class of compounds using greener and cleaner methods is of high interest. In a model reaction using iron or manganese as catalytic center, acetic acid is necessary to facilitate the oxygen atom transfer on the substrate [1]. In order to suppress or reduce the acetic acid used in the reaction, two strategies have been developed and presented herein. The first one is to associate a metal center (Fe or Mn) and a robust nitrogen based ligand functionalized with H-bond donor groups that have been shown to activate H2O2 [2], more particularly fluoroalcohol groups [3]. The second strategy developed is to replace the acetic acid, replacing it by silica nanoparticles functionalized with carboxylic functions [4,5]. From those nanoparticles, it is possible to partially deprotonate the carboxylic acid functions, obtaining a particle with carboxylic acids and carboxylate functions, replacing the acetic acid and being able to immobilize through coulombic interaction the cationic catalyst at the surface of the nanoparticles. This strategy will also give access to recyclable catalysts and process using less volatiles. References [1] O. Cussó, X. Ribas, M. Costas, Chem. Commun. 2015, 51, 14285--14298. [2] K. Neimann, R. Neumann, Org. Lett., 2000, 2, 2861–2863. [3] P. Guillo, J.-C. Daran, E. Manoury, R. Poli, ChemistrySelect 2017, 2, 2574–2577. [4] W.Dexuan, L. Guian, H. Qingyan, W. Ziqiang, P. Liping, Z. Zhonayue, Z. Hairong, J. Nanosci. Nanotechnol. 2016, 16, 3821–3826. [5] J. Bu, R. Li, C. W. Quah, K. J. Carpenter, Macromolecules 2004, 37, 6687–6694.

38

O24. Efficient Pentafluoroethylation of Allyl and Benzyl Halides with TMSCF3-Derived CuC2F5. Mechanistic Insights Jordi Mestre,1 Sergio Castillón,1 and Omar Boutureira1

1 Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, C/Marcel·lí Domingo 1, 43007 Tarragona, Spain, jordi.mestre@urv.cat.

Numerous reports highlight the importance of incorporating fluorinated modifications into drug candidates to boost their efficiency.[1] Massive research on trifluoromethylation reactions promoted plenty of strategic protocols and commercially available reagents.[2] In contrast, the introduction of pentafluoroethyl units, which sometimes provides the best bioactive properties, is largely underdeveloped.[3] We report a convenient, easy and inexpensive preparation of simple but highly active ligandless CuC2F5 species towards allylic and benzylic pentafluoroethylation. The mechanism of this transformation has systematically been investigated with a combination of experimental and theoretical methods.

[1] a) Y. Zhou, J. Wang, Z. Gu, S. Wang, W. Zhu, J. L. Aceña, V. A. Soloshonok, K. Izawa and H. Liu, Chem. Rev. 2016, 116, 422-518; b) S. Purser, P. R. Moore, S. Swallow and V. Gouverneur, Chem. Soc. Rev. 2008, 37, 320-330. [2] a) O. A. Tomashenko and V. V. Grushin, Chem. Rev. 2011, 111, 4475-4521; b) X. Yang, T. Wu, R. J. Phipps and F. D. Toste, Chem. Rev. 2015, 115, 826-870. [3] a) A. Lishchynskyi, V. V. Grushin, J. Am. Chem. Soc. 2013, 135, 12584-12587; b) H. Serizawa, K. Aikawa, K. Mikami, Org. Lett. 2014, 16, 3456-3459.

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40

O25. Study of VC-based catalysts for CO2 conversion to CO

Pajares A.1,2, Ramirez de la Piscina P.1, Homs N.1,2*

41

POSTERS

42

PS1. Isotopic labeling for the evaluation of drug candidates catalyzed by metallic nanoparticles

D. Bouzouita1, S. Tricard1, L. Martinez-Prieto1, G.Lippens2 and B. Chaudret1 1 LPCNO, INSA, CNRS, Université de Toulouse, 135 avenue de Rangueil, 31077 Toulouse, France,

bouzouit@insa-toulouse.frl. 2 Affiliation 2, address 2.

Labeled compounds are of great interest in chemistry. They are used to do mechanistic studies in organic and organometallic chemistry. They could be used as internal standards for mass spectroscopy or in pharmacology, labeled molecules could also enhance the pharmacokinetic properties of a drug. For these reasons, my thesis focus on the direct labeling of molecules with biologic interest and more precisely on the direct H/D exchange using different type of nanoparticles as catalysts. The main goal of the PHD project is the synthesis of novel nanoparticles for isotopic exchange (H/D or H/T). In the first part it was important to develop a new class of water soluble ruthenium nanoparticles. Then in a second part different types of nanoparticles (bi-metallic nanoparticles or made of other metals nanoparticles) were prepared in order to modulate the selectivity and the activity of the nanoparticles in H/D exchange Ruthenium nanoparticles stabilized by NHC (N-heterocyclic carbene) were prepared, as this family of ligand provides a strong coordination with the NPs. Another advantage of the NHC ligands is the possibility to modify their radicals and thus to tune their physical properties. In this way, sulfonated NHC have been used to synthesize water soluble ruthenium nanoparticles. Then, bimetallic nanoparticles have been prepared in order to tune the chemical order of the NPs and thus influence the H/D exchange process. As the ruthenium is very active and could decompose or reduce some substrates and the platinum is nor active in the H/D exchange, Ru-Pt nanoparticles were synthetized to modulate the reactivity of there Ru nanaoparticles. Different nanoparticles were synthetized using three different platinum precursors (Pt(NBE)3, Pt(CH3)2COD and Pt2(dba)3. And the results showed that we could modulate the reactivity of these catalysts and also the selectivity. References [1] B. Rousseau, B. Chaudret et al. Angew. Chem. Int. Ed., 2014, 53, 230-234. [2] G. Pieters et al. Angew. Chem. Int. Ed., 2015, 54, 10474-10477. [3] L. Martinez-Prieto et al. Angew. Chem. Int. Ed., 2017, 53, 5850-5853.

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PS2. Ensemble effect in Ru@C60 hydrogenation catalysts

C. Rivera-Carcamo1, M.R. Axet1, P. Serp1 1 Laboratoire de Chimie de Coordination - CNRS, Composante ENSIACET, 4 alléeEmile Monso, BP 44099, 31030

Toulouse Cedex 4, France. E-mail: camila.rivera@lcc-toulouse.fr

Fullerides are nanostructured arrangements formed by the interaction between fullerene (C60) and metals. In the past years the study of differents alkali-fullerides[1] have been largely developped, in contrast to the limitated number of reports about transition metal-fullerides. Previous results indicates that the choice of the solvent is a key parameter to control the structure of these materials.[2] In this context, we have produced Ru@C60 by decomposition of [Ru(COD)(COT)] under dihydrogen in the presence of C60 and using different mixture of solvents. Scanning transmission electron microscopy with high-angle annular dark-field imaging (STEM-HAADF) show that Ru species can be modulated related to the solvent used, from individual atoms to small clusters (Figure1), thus modifyng the properties of the synthetized material.

Figure 1. STEM-HAADF of Ru@C60 (molar ratio 20:1): a) synthetized in pure toluene; b) synthetized in mixture toluene/methanol 95:5; and c) synthetized in mixture toluene/dichloromethane 95:5. Those Ru@C60 materials were characterized by Raman spectroscopy, XPS, STEM-HAADF, WAXS and EXAFS, and tested as catalyst in the reaction of hydrogenation of nitrobenzene. The results suggested that the catalytic activity and selectivity is influenced by the presence or not of Ru-Ru bonds in the catalysts. References [1] D. Murphy, M. Rosseinsky, R. Fleming, R. Tycko, A. Ramirez, R. Haddon, T. Siegrist, G. Dabbagh, J. Tully, R. Walstedt, Journal of Physics and Chemistry of Solids, 1992, 53 1321-1332. [2] F. Leng, I.C. Gerber, P. Lecante, W. Bacsa, J. Miller, J.R. Gallagher, S. Moldovan, M. Girleanu, M.R. Axet, P. Serp, RSC Advances, 2016, 6, 69135-69148.

a) T-Ru@C60

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PS3. Bimetallic nanoparticles in glycerol : Structure & surface reactivity

T. Dang Bao1, I. Favier1, M. Gómez1 1 Laboratoire Hétérochimie Fondamentale et Appliquée, UMR CNRS 5069, Université de Toulouse 3 - Paul

Sabatier, 118 route de Narbonne, 31062 Toulouse, France, favier@chimie.ups-tlse.fr Bimetallic nanoparticles (BMNPs) represent attractive catalytic systems thanks to the synergy between both partners; the addition of a “guest” to a “host” metal in a same entity could modify its electronic properties (by charge transfer, orbital hybridization…) and/or structure (alloy, core shell...) [1-2]. Therefore, we were interested in the synthesis of BMNPs with the aim of improving the activity and to better control the selectivity in catalysis. In our group, we have previously described the synthesis of monometallic Pd(0)NPs and Cu(0)NPs in glycerol [3-4]. In this present work, we were interested in the synthesis of Pd-Cu BMNPs following two main strategies: co- and sequential reduction. Under these conditions, only co-reduction processes permitted the obtention of BMNPs.

These BMNPs were characterized by different techniques : PXRD, FT-IR, XPS, cyclic voltammetry, elemental analysis, HR(TEM), HAADF-STEM, and EDX (mapping and line-scanning profiles). Depending on the Pd/Cu ratio used, Pd/Cu = 1/1 gave PdNPs coated by a non-uniform Cu-shell, Pd/Cu = 1/2 gives random alloys and Pd/Cu = 2/1 gives mainly mixture of monometallic PdNPs and CuNPs. These structures were also confirmed by their reactivity in Pd-catalyzed hydrogenation of alkynes and Cu-catalyzed azide-alkyne cycloaddition (CuAAC). Pd1Cu1 NPs were also applied in one-pot processes acting as multi-task catalytic system for sequential CuAAC and Pd-catalyzed C-C cross coupling (Sonogashira, Suzuki and Heck) reactions. References [1] F. F. Tao, Chem. Soc. Rev., 2012, 41, 7977–7979. [2] T. Dang-Bao, D. Pla, I. Favier, M. Gómez, Catalysts 2017, 7, 207. [3] F. Chahdoura, C. Pradel, M. Gómez, Adv. Synth. Catal., 2013, 355, 3648-3660. [4] T. Dang-Bao, C. Pradel, I. Favier, M. Gómez, Adv.Synth. Catal. 2017, 359,2832-2846.

45

PS4. Bio-Sourced Deep Eutectic Solvents and ScCO2: Innovative Media for Metal-Based Nanocatalysts

G. Garg1,2, A. M. Masdeu-Bultó3, Y. Medina-Gonzalez1, M. Gómez2 1 Laboratoire de Génie Chimique, Université de Toulouse, INPT, UMR CNRS 5503, 4, Allée Emile Monso, 31030

Toulouse, e-mail : garima.garg@ensiacet.fr 2 Laboratoire Hétérochimie Fondamentale et Appliquée, UMR CNRS 5069, Université de Toulouse 3 - Paul Sabatier, 118 route de Narbonne, 31062 Toulouse 3 Department of Physical and Inorganic Chemistry, N4 Building - Universitat Rovira i Virgili. Campus Sescelades. Marcel·lí Domingo s/n. - 43007 - Tarragona Spain A great obstacle encountered during the development of green chemical processes and separations is the use of specific solvents for particular steps. Solvent engineering, allowing triggering changes in solubility and physicochemical properties of the solvent, increasing efficiency and decreasing energy consumption. My PhD project represents an effort to develop green versatile catalytic systems based on the coupling of green bio-sourced deep eutectic solvents (DESs), with supercritical CO2 (scCO2) in a biphasic system. This approach will permit: 1) Engineering the transport and solvency properties of the DES phase by controlling the CO2 concentration by pressure [1]; 2) to prepare metallic nanoparticles in the DES phase [2]; 3) to improve the solubility and diffusion of H2; and 4) to extract the products from the catalytic phase by scCO2 avoiding the use of additional organic solvents. Therefore we plan to synthesize DES using the combination of amino acid-based choline salts with glycerol as hydrogen bond donor, exhibiting interesting properties such as negligible vapor pressure and high solubility effects on chemicals. In the field of metal-mediated reactions, MNPs prepared in glycerol exhibit excellent catalytic properties, as proven by our team [3,4]. In this contribution, we present the synhtesis and characterization of PdNPs by polyol methodology stabilized by choline-amino acid based ionic liquids in glycerol. The as-prepared PdNPs have shown remarkable catalytic activity in hydrogenation processes of a variety of substrates (alkynes, alkenes, nitro-aromatic derivatives and benzaldehydes). However, one of the major drawbacks of DES are their high viscosities, which hinders mass transport. In these DES/CO2 coupled systems, CO2 is expected to improve the transport properties of the DES phase.We have been able to decrease the viscosity of the DES under high pressure of CO2. This DES/CO2 phase has been studied by innovative micro-rheological techniques by using molecular rotors. References [1] Y. Medina-Gonzalez, T. Tassaingc, S. Camya and J.-S. Condoret, J. Supercrit. Fluids, 2013, 73, 97-107. [2] C. Oumahia, J. Lombarda, S. Casalea, C. Calersa, L. Delannoya, C. Louisa and X. Carrier, Catal. Today, 2014,

235, 58-71. [3] F. Chahdoura, C. Pradel and M. Gómez, Adv. Synth. Catal., 2013, 355, 3648-3660. [4] A. Reina, C. Pradel, E. Martin, E. Teuma and M. Gómez, RSC Adv., 2016, 6, 93205-93216.

46

PS5. Stabilization of ultra-small ruthenium nanoparticles by ethanoic acid

R. González-Gómez1,2, L. Cusinato2, I. del Rosal2, C. Amiens1, R. Poteau2, K. Philippot1.

1 LCC-CNRS, Université de Toulouse, UPS, 205 route de Narbonne, BP 44099, F-31077-Toulouse Cedex 4, France. roberto.gonzalez@lcc-toulouse.fr.

2 LPCNO (IRSAMC), Université de Toulouse ; INSA, UPS ; CNRS (UMR 5215); Institut National des Sciences Appliquées, 135 avenue de Rangueil, F-31077 Toulouse, France.

The interest in metal nanoparticles (MNPs) continues to be very strong in both academic and industrial domains owing to their applications in several fields.[1] Properties of MNPs are usually different to those of matter and molecular transition metal complexes. This relies on an electronic structure intermediate between the quantized levels in finite-size small compounds and the band structure in solids. MNPs properties depend on their shape, size, defects and nature and surface coverage rate of ligands.

Regarding ruthenium nanoparticles (RuNPs), they have been reported to be stabilized by amines, phosphines, carbenes, alcohols, etc.[2] Despite this diversity, there is still a need to modify their surface in order to improve their. Although carboxylic acids are widely used as surfactants in colloids synthesis, to our knowledge the adsorption of carboxylic acids RCOOH (R≠H) on metal surfaces have received less attention.

For this purpose, we started studying the surface properties of RuNPs stabilized by carboxylic acids as a model in order to bring an understanding of structure/property relationships at the nanoscale. The RuNPs were synthesized following the organometallic approach [3] using ethanoic acid as a stabilizer. The surface state of these RuNPs has been probed by IR and NMR techniques leading to a mapping of their surface. In parallel, DFT calculations have been performed according to a thermodynamic model [4] fed with DFT energies. Also, it has been carried out a systematic analysis of the bond properties and of the electronic states (Density of States, Crystal Orbital Hamilton Population, atomic charges). As it will be presented, the experimental and theoretical results are in good agreement making it thus a first step to build a model to understand the ligand influence on MNPs properties. References [1] G. Schmid, Ed. Nanoparticles. From theory to applications, 2nd ed.Wiley-VCH: Weinheim, Germany, 2010 [2] L. M. Martínez-Prieto and B. Chaudret, Organometallic Ruthenium Nanoparticles: Synthesis, surface Chemistry, and Insights into Ligand Coordination, Acc. Chem. Res., 2018. [3] C. Amiens, D. Ciuculescu-Pradines and K. Philippot, Coord. Chem. Rev., 2016, 38, 409-432. [4] L. Cusinato, L. M. Martínez-Prieto, B. Chaudret, I. Del Rosal and R. Poteau, Nanoscale, 2016, 8, 10974-10992

47

PS6. Remarkable catalytic activity of gel-trapped palladium nanoparticles in flow chemistry using a polymeric membrane reactor.

M.López Viveros1, I. Favier2, M. Gómez2, J.F. Lahitte1, J.C. Remigy1 1 Laboratoire de Génie Chimique, Université de Toulouse, CNRS, INPT, UPS, Toulouse, France. 2 Laboratoire Hétérochimie Fondamentale et Appliquée, UMR CNRS 5069, ICT, UPS, Toulouse, France.

Flow chemistry presents several advantages over batch reactors, such as efficient heat and mass transfer which allows an increase in the reaction rate and therefore productivity. In particular, flows through reactors containing immobilized catalyst have the supplementary advantage of not requiring catalyst separation from products. [1]

Palladium nanoparticles (PdNP) are widely known catalyst for their high efficacy on C-C coupling and selective hydrogenation reactions of industrial interest. Immobilization and stabilization of PdNP by intermatrix synthesis within a polymeric gel grafted into the surface of a membrane support is presented here. Reactions are carried out continuously in a flow through configuration as an efficient way to address industrial applications.

The performance of catalytic membranes have been studied in the reaction of (i) Suzuki-Miyaura cross-coupling between 1-iodo-4-nitrobenzene and phenylboronic acid followed by the hydrogenation of 4-nitrobiphenyl and (ii) hydrogenation of 4-nitrobenzene by a H2 saturated solution using a hollow membrane contactor. Reactions were carried out by filtering the solution containing the reactants in a flow through configuration. Full conversion and high selectivity for both reactions were achieved after short residence times (less than one minute). Neither leaching nor deactivation of PdNP were detected after 8-10 runs. Experiments from present and previous works [2],[3] show that catalytic membranes are much more efficient when compared to batch reactors or colloidal nanoparticle systems.

References [1] R. Porta, M. Benaglia, and A. Puglisi. Org. Process Res. Dev.2016. vol. 20, no. 1, pp. 2–25. [2] C. Emin, J. Remigy, and J. Lahitte. 2014. J. Memb. Sci., vol. 455, pp. 55–63. [3] Y. Gu, I. Favier, C. Pradel, D. L. Gin, J.-F. Lahitte, R. D. Noble, M. Gómez, J.-C. Remigy. 2015. J. Membrane Sci., vol. 492, pp. 331–339.

48

PS7. Cobalt catalysts on carbon based materials for Fischer-Tropsch synthesis

A. Ghogia1,2,3, D. Pham Minh1, P. Serp2, K.Soulantica3, A.Nzihou1 1Université de Toulouse, IMT Mines Albi, UMR CNRS 5302, Centre RAPSODEE, Campus Jarlard, F-81013 Albi,

cedex 09, France. aghogia@mines-albi.fr 2LCC, CNRS-UPR 8241, ENSIACET, Université de Toulouse, France. 3LPCNO, CNRS-UMR5215, INSA Toulouse, Toulouse, France. In recent decades, there has been an increase in global energy consumption due to rapid population growth and industrial development[1]. In order to meet this growing demand for energy, Fischer-Tropsch synthesis (FTS) for converting syngas (mixture of CO and H2) into liquid fuel has attacted a lot of interest,proposing gas conversion as a major solution to reduce the exploitation of petroleum resources. Generally, for the FTS the catalyst is composed of an active phase such as Co or Fe dispersed on conventional supports such as SiO2, Al2O3, TiO2, ZrO2, or MgO[2]. A drawback of these supports is their reactivity toward cobalt, which during catalyst preparation or catalysis results in the formation of hard to reduce mixed compounds. To avoid these problems, the use of carbon materials is appealing since they offer the advantage of being stable at high temperature, do not lead to strong metal-support interaction, and have a high surface area ,which leads to significantly enhanced activity and selectivity of the catalyst during FTS[3].In this work, we intend to investigate textural and, structural properties of cobalt catalysts supported on carbon nanotubes (CNTs), nanofibers of small (CNFp) and large (CNFg) diameters,as well as fibrous material (FM) (Fig.1) and to investigate their catalytic performances in fixed-bed FTS.

Figure.1. TEM image : a) 15.0 wt% Co/fibrous material catalyst; b) 15.0 wt% Co/nanofibers of large diameter catalyst. References [1] Energy consumption in the UK and the world, (2013) 1–10. [2] R.C. Reuel, C.H. Bartholomew,J. Catal. 85 (1984) 78–88. [3] A. Tavasoli, M. Irani, A. Nakhaeipour, Y. Mortazavi, A.A. Khodadadi, A.K. Dalai, J. Chem. Chem. Eng. 28 (2009)

37–48.

49

PS8. Structure-synthesis relationship study of colloidal PdNPs using designed experiments

O.Benkirane1,2, J. Delgado1,2, J. Ferré2, D. Curulla-Ferré3, C. Claver1,2, C. Godard1,2

1 Centre Tecnològic de la Química, Edifici N5. C/ Marcel.lí Domingo, 43007 Tarragona, olivia.benkirane@ctqc.org 2 Universitat Rovira i Virgili, Edifici N4. C/ Marcel.lí Domingo, 43007 Tarragona 3 Research & Technology Feluy, Zone Industrielle Feluy C, B7181 Seneffe, Belgium

Colloidal chemistry is a great tool for the fabrication of well-defined metal nanocatalysts since it allows the precise control of their size, shape structure and composition. Such a control enables a maximization of the available metal surface area and thus can improve the catalyst productivity.[1] However, the metal NPs synthesis depends on a wide variety of parameters which make complex and time consuming the experimental research when the strategy is a variation at One-Factor-At-a-Time (OFAT). Another alternative is the use of Design Of Experiments (DOE). This chemiometric tool provides mathematical and statistical frameworks that guide an optimal planning of experiments by the variation of all factors simultaneously. In this way, it is possible to obtain the desired information with a reduced number of experiments, in other words, with the maximum efficiency.[2-4]

The objective of this work is to study via designed experiments the effect of the synthetic parameters and combinations of them on the formation of Pd NPs synthesized by chemical reduction. The key parameters and interactions will be highlighted as well as the possibility to form well-defined NPs with different size. This study plan to be an example of application of DOE methodology for the synthesis of NPs and aims to demonstrate its high potential.

TEM images of Pd NPs after treatment with Fiji software

Representation of the sample homogeneity in terms of size (left side) and shape (right side) via a color scale References [1] Odom, T. W.; Pileni, M.-P. Nanoscience,Acc. Chem. Res. 2008, 41, 1565 [2] Box, G. E. P.; Hunter, W. G.; Hunter, J. S. Statistics for Experimenters, 2nd ed., 2005 [3] Esbensen, K. H.; Guyot, D.; Westad, F.; Houmoller, L. P. Multivariate data analysis; 5th ed.; CAMO ASA, 2001 [4] Ferré, J.; Rius, F. X. Introducción al diseño estadístico de experimentos,Técnicas de laboratorio 2003, 24

50

PS9. Synthesis of monometallic Ni, Cu, Pd and bimetallic NiCu and PdCu NPs on carbon nanotubes as nanocatalysts for selective

hydrogenation reactions Jorge A. Delgado,1 Diego Lomelí,2 Miriam Diaz de los Bernardos,1 Sara Perez-

Rodriguez,3 Aitor Gual,1 Carmen Claver,4 Cyril Godard,4 1 Centre Tecnològic de la Química, Tarragona, Spain. jorge.delgado@ctqc.org 2 Universidad de Guadalajara, Guadalajara, Mexico 3 Instituto de Carboquímica, Zaragoza, Spain 4 Universitat Rovira i Virgili, Tarragona, Spain The decomposition of organometallic metal complexes in the presence of stoichiometric amounts of ligands have demonstrated to be an effective method for the preparation of welldefined metal nanoparticles under mild conditions.[1] Very recently, a new procedure for synthesizing small and well-defined NHC-stabilized NiNPs has been developed.[2] This methodology permitted the preparation of not only colloidal nanoparticles but also the direct immobilization on carbon nanotubes by a simple ‘‘one-pot’’ procedure. The supported Ni NPs/CNTs revealed to be efficient catalysts in the selective hydrogenation of internal alkynes into the corresponding (Z)-alkenes. In the present contribution, the preparation of monometallic nanoparticles of other metals (Cu, Pd) as well as bimetallic mixtures of them (NiCu, and PdCu) is presented, thus demonstrating the versatility of the reported methodology. The bimetallic structure of the prepared materials was studied by XRD, HRTEM, and STEM-EDX. The reactivity of the supported M/CNTs catalysts was evaluated in hydrogenation reactions, evidencing the positive effect of the promoting metal in terms of the product selectivity.

Preparation of M/CNTS (M = Ni, Cu, Pd, NiCu, NiPd) as nanocatalysts for selective

hydrogenation reactions

References

[1] P. Lara, O.Rivada-Wheelaghan, S. Conejero, R. Poteau, K. Philippot, B. Chaudret, Angew. Chem. Int. Ed. 2011, 50, 12080.

[2] M. D. de los Bernardos, S. Perez-Rodriguez, A. Gual, C. Claver, C. Godard, Chem. Commun. 2017, 53, 7894.

51

PS10. Immobilized rhodium catalysts for asymmetric hydroformylation under batch and flow conditions

Anton Cunillera1, Cyril Godard1, Aurora Ruiz1 and Carmen Claver1,2 1 Universitat Rovira i Virgili, Centre Tecnològic de Química, carrer Marcel·lí Domingo s/n, Tarragona, 43007, Spain 2 Centre Tecnològic de la Química, Marcel·lí Domingo s/n, Campus Sescelades, 43007 Tarragona, Spain.

anton.cunillera@urv.cat

Hydroformylation of alkenes is one of the most important industrial applications of homogeneous catalysis. Diphosphite ligands have been successfully studied in the rhodium catalysed hydroformylation due to their modular nature [1]. Homogeneous catalysts however present the disadvantage of recycling and reuse. The development of supported catalysis is therefore required to ensure the sustainability of the catalytic processes. The use of non-covalent interactions is an attractive strategy to attach homogeneous catalysts onto a solid support since it usually does not require additional synthetic efforts. Through this approach the structure of the ligand moiety is maintained. [2] Carbon materials emerged as promising supports due to their unique properties and large surface area.[3] Furthermore, they provide the possibility to immobilise catalysts by π-π stacking, which allow the grafting of molecules containing large polyaromatic systems.[4] In this work, we report rhodium complexes bearing pyrene tagged chiral 1,3-diphosphite ligands. The non-covalent immobilisation of these species onto carbon nanotubes was explored to obtain heterogenised catalysts, which were subsequently tested in the asymmetric hydroformylation of bicyclic alkenes [5]. Recycling experiments in batch and flow mode were carried out to analyse the robustness of these systems. References [1] van Leeuwen, P. W. N. M.; Kamer, P.; Claver, C.; Pàmies, O.; Diéguez, M. Chem. Rev. 2011, 111, 2077. [2] García, J. I.; Mayoral, J. A.; Fraile, J. M.; Chem. Rev. 2009, 109, 360. [3] Tasis, D.; Tagmatarchis, N.; Bianco, A.; Prato, M. Chem. Rev. 2006, 106, 1105. [4] a) Vriamont, C.; Devillers, M.; Riant, O.; Hermans, S. Chem. Eur. J. 2013, 19, 12009, b) Sabater, S.; Mata, J.; Peris, E. Organometallics, 2015, 34, 1186 [5] Nozaki, K.; Takaya, H.; Hiyama, T. Top. Catal. 1997, 4, 175.

52

PS11. Study of THFA production from furfural using hectorite supported Ni, Cu or Ni-Cu catalysts

V. Sánchez 1, P. Salagre1, Y. Cesteros1

1Universitat Rovira i Virgili, Departament de Química Física i Inorgànica, C/ Marcel·lí Domingo s/n, 43007 Tarragona, Spain vladimir.sanchez@urv.cat

Furfural is a chemical platform obtained from biomass that can be catalytically hydrogenated to obtain tetrahydrofurfuryl alcohol (THFA) via Scheme 1. This process can be catalysed by metals such as Ni [1]. However, the presence of acid sites should be avoided since can led secondary reactions [2].The presence of Cu in Ni catalysts could modify their catalytic behaviour [3].. Hectorite is a clay with a modulable acidity during the synthesis [4]. We propose the use of Ni, Cu and Ni-Cu catalysts supported on a hectorite (H) without acidity to study the influence of Ni and Cu as metal phases on the catalytic hydrogenation of furfural to THFA.

(H) was synthesized following literature(327 m2/g of BET area) [4].40 wt% Ni (NiH), Cu(CuH) and Ni-Cu catalysts were prepared by impregnation, calcination and reduction. Ni-Cu catalysts were prepared at molar ratios of 6:1 (Ni-Cu6H) and 1:1 (Ni-Cu1H). An aqueous solution of furfural was added to a bath reactor with the catalyst. 140 ºC, 40 bar of H2 and stirring were mantained for 4 h. The productswas analyzed by GC. Catalysts were characterised by TPR and XRD.

XRD patterns of Ni-Cu catalysts showed the presence of Ni-Cu alloy, in higher amounts for Ni-Cu1H. The reaction products detected were only FOL and THFA (Figure 1). All catalysts with Cu presented total conversion. FOL was only detected for catalyst NiH. Selectivity to THFA was near to 100% only when Ni-Cu1H was used with an overall yield to THFA of 95%.

Acknowledgments – The authors are grateful for the financial support of the Ministerio de Educación y Ciencia of Spain and FEDER funds (CTQ2015-70982-C3-3-R).

References [1] Y. Nakagawa, H. Nakazawa, H. Watanabe and K. Tomishige, ChemCatChem,2012, 4(11), 1791.

[2] Y. Yang, Z. Du, Y. Huang, F. Lu, F. Wang, J. Gao and J. Xu, Green Chem., 2013, 15(7), 1932.

[3] F.B. Gebretsadik, J. Llorca, P. Salagre and Y. Cesteros, ChemCatChem, 2017, 9, 1

[4] T. Sánchez, P. Salagre, Y. Cesteros, Microporous and Mesoporous Materials, 2013, 171, 2

OO

Furfural Tetrahydrofurfuryl alcohol (THFA)

OOH

H2 Supported metal

catalyst

H2 Supported metal

catalyst

OOH

Furfuryl alcohol (FOL)

Scheme 1. Hydrogenation of furfural to THFA via FOL.

Conv. THFA yield

53

PS12. Photo-H2 Production by Nickel- and Cobalt-Metal Complexes Based on a Pyridinophane Ligand

P. Guillo,1,2 E. Giannoudis,4,5 Y. Wang,1,2 J.-C. Daran,1,3 M. Chavarot-Kerlidou,4 D.

Agustin,1,2 V.Artero,4 A. G. Coutsolelos,5 E. Manoury,1,3 R. Poli,1,3 1 CNRS, Laboratoire de Chimie de Coordination, Toulouse, France 2 Université de Toulouse, Institut Universitaire de Technologie Paul Sabatier, Castres, France. 3 Université de Toulouse, UPS, INPT, Toulouse Cedex 4, France 4 Laboratoire de Chimie et Biologie des Métaux, Université Grenoble Alpes, CEA, CNRS, 17 rue des Martyrs, 38000 Grenoble, France 5 Laboratory of Bioinorganic Chemistry, Department of Chemistry, University of Crete, Voute Campus, 70013 Heraklion, Crete, Greece. E-mail: pascal.guillo@iut-tlse3.fr Control of the factors that govern the reactivity of a metal complex is crucial in homogeneous metal-based catalysis. It is usually assumed that the reactivity of a metal center is mainly dictated by the interaction between the metal center and its primary coordination sphere. In Nature, in addition to the first coordination sphere, the second coordination sphere also plays an important role. In hydrogenase metalloenzymes the presence of proton relays is essential for the efficient reduction of H+ into H2.[1] In this project, we are interested in developing new catalytic systems possessing in their second coordination sphere functional groups able to interact with different kind of substrates to enhance the catalytic activity of the targeted reactions. Notably, we designed ligands decorated in the second coordination sphere by hydroxyl groups that have F substituents in their proximity.[2] First row metal complexes (metal = cobalt and nickel) have been obtained and tested for proton reduction under phtochemical conditions. It was expected that the combination between the H-bonding network in the second coordination sphere (due to the fluoroalcohol groups) and the metal center enhance the proton reduction, the fluoroalcohol groups acting as proton relays.

References [1] T. R. Simmons, G. Berggren, M. Bacchi, M. Fontecave, V. Artero, Coord. Chem. Rev. 2014, 270-271, 127-150 [2] P. Guillo, J.-C. Daran, E. Manoury, R. Poli, ChemistrySelect 2017, 2, 2574-2577

54

PS13. Metal-Based Nanomaterials as Catalyst for Water Splitting I. Álvarez-Prada,1 J. Muñoz,1,2 L. Escriche,1 K. Philippot,3,4 X. Sala,1 N. Romero,1 J.

García-Antón1

1 Departament de Química Universitat Autònoma de Barcelona, Cerdanyola del Vallès, E-08193 Barcelona, Spain, luisignacio.alvarez@uab.cat

2 ICMAB-CSIC, Campus UAB, Cerdanyola del Vallès, E-08193, Barcelona, Spain 3 LCC-CNRS, 205 Route de Narbonne, BP 44099, F-31077 Toulouse Cedex 4, France. 4 Université de Toulouse, UPS, INPT, LCC, F-31077 Toulouse, France.

Photocatalytic water splitting is a process in which oxygen and hydrogen are generated,[1] and offers an attractive method to store renewable energy in the form of chemical bonds. Hydrogen is so far an alternative to fossil fuels, non renewable and poluting.

A fully efficient system for water splitting requires a catalyst with high activity and stability. For this purpose, metal nanoparticles are an interesting option, which can be formed often by decomposition of homogeneous catalysts, and that have been confirmed as the true active species in many of these systems.[2]

Platinum and ruthenium nanoparticles are among the most studied catalytic systems in this area.[3] However, its high cost has motivated the interest to study other metals such as copper, more abundant and affordable.[4] In the present work, a series of nanoparticle systems have been prepared, based on both ruthenium and copper, with the aim of studying their electrochemical behavior, and thereby determine the suitability of these materials as catalysts in the water splitting reaction.

References [1] 1. Water Oxidation. R. Bofill, J. García-Antón, L. Escriche, X. Sala, A. Llobet In: Comprehensive Inorganic Chemistry, II, eds. Reedijk, J & Poeppelmeier, K.; Elsevier, 2013, 8, 505 [2] H. Junge, et al., Chem. Eur. J. 2012, 18, 12749. [3] Y. Zheng, Y. Jiao, Y. Zhu, L. Hua Li, Y. Han, Y. Chen, M. Jaroniec, S. Qiao, J. Am. Chem. Soc., 2016, 138, 16174−16181 [4] J. Du, Z. Chen, S. Ye, B. Wiley, T. Meyer. Angew. Chem. Int. Ed., 2015, 54, 2073 –2078

55

PS14. Co(OH)2 Nanoparticles Supported on Carbon Fibers as Electrocatalysts for the Oxygen Evolution Reaction

L. Mallón,1,2 A. Moya,3 R. Más-Ballesté,3 J. Alemán,3 J. García-Antón,1 R. Bofill,*,1 X. Sala,*,1 K. Philippot*,2

1 Departament de Química, Universitat Autònoma de Barcelona, Cerdanyola del Valles, 08193 Barcelona, Spain. laura.mallon@uab.cat

2 LCC-CNRS, Université de Toulouse, CNRS, UPS, 205 Route de Narbonne, 31077 Toulouse Cedex 4, France. 3 Universidad Autónoma de Madrid, Ciudad Universitaria de Cantoblanco, 28049 Madrid, Spain.

High consumption of fossil fuels together with the accumulation of CO2 in the atmosphere [1] due to their combustion have put forward the urgent need for a cheap, clean and carbon free energy source. One of the most attractive and feasible solutions to this challenge is the production of H2 by the splitting of water photo-activated by sunlight, thus mimicking green plants, algae and cyanobacteria, in the so-called artificial photosynthesis [2]. In this redox process, water is oxidized to dioxygen in the anode (Eq. A), constituting the source of electrons to reduce protons to dihydrogen in the cathode (Eq. B).

2H2O O2 + 4H+ + 4e- (A) 2H+ + 2e- H2 (B)

Both molecular complexes and metal oxides are efficient catalysts for the oxygen evolution reaction (OER, Eq. A) and hydrogen evolution reaction (HER, Eq. B), but given their proved stability and high surface per volume ratio, nanoparticulate metal oxides are the chosen option in this work. From an engineering point of view, supported catalysts which can act themselves as electrode materials are interesting systems. Therefore, the integration of metal-oxide electrocatalysts with conductive carbon-based supports such as graphene, carbon nanotubes or carbon fibers is of current interest, being also a way to improve their tipically low conductivity. Cobalt-based nanoparticles are synthesized by the decomposition of an organometallic cobalt precursor under H2 in the presence of a carbon fiber brush (CFs), acting both as support and stabilizer, leading to nanoparticles in a size range 2-4 nm on the CFs surface. The obtained nanomaterials are characterized by complementary techniques including TEM, ICP-OES, XPS and electrochemical analyses. Results obtained with CFs-supported materials have shown an onset overpotential ƞ0≈400 mV and a Faradaic efficiency of ≈70% towards the OER in basic conditions. References [1] International Energy Agency. https://www.iea.org. [2] H. Zhou, R. Yan, D. Zhang, T. Fan, Chem. Eur. J, 2016, 22, 9870-9885. [3] C. Amiens, D. Ciuculescu-Pradines, K. Philippot, Coord. Chem. Rev. 2016, 308, 409-432.

56

PS15. Solar-driven water splitting: from molecular catalysis to photoelectrochemical cells

S. Grau1, M. Ventosa1, N. Jameei Moghaddam1, Y. Shi1,2, W. Cambarau1, T.-Y. Hsieh1, E. Palomares1, M. Lanza2, C. Gimbert-Suriñach1 and A. Llobet1,*

1 Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans, 16, 43002, Tarragona, Spain,* allobet@iciq.es

2 Institute of Functional Nano & Soft Materials, Collaborative Innovation Center of Suzhou Nanoscience and Technology, Soochow University, Suzhou, 215123, China

Water reduction and water oxidation catalysts are the core of light-induced water-splitting devices. Current designs are based on metals such as Pt or Ni for the hydrogen evolution reaction (HER) and metal oxides for the oxygen evolution reaction (OER)1. In the recent years, molecular catalysts for HER and OER have been developed, with well understanding of the mechanisms of the catalytic reactions2. Furthermore, molecular catalysts have the potential to tune their activity and robustness by modifying the ligands in the coordination sphere. The following step is to functionalize the best molecular catalysts in a complete photoelectrochemical cell (PEC)3,4. The key elements to build a solar-driven water spliting are: a) a light harvesting unit that will be based on an oxide and/or graphitic (semi)conductor; b) molecular catalysts for both water oxidation and proton reduction reactions attached at the surface of a); and c) PEC optimization by combining all these elements. In this work, recent advances towards a solar-driven water splitting device containing molecular complexes for hydrogen evolution and water oxidation catalysis will be presented (Fig1).

Fig1. Schematic design of a HER molecular catalyst in a photoelectrochemical device.

References [1] J. R. McKone, N. S. Lewis, H. B. Gray, Chem. Mater. 26, 407 (2014) [2] S. Berardi, S. Drouet, L. Francàs, C. Gimbert-Suriñach, C. Richmond,T. Stoll, A. Llobet, Chem. Soc. Rev. 43, 7501 (2014) [3] Creus, J., Matheu, R., Peñafiel, I., Moonshiram, D., Blondeau, P., Benet-Buchholz, J., Llobet, A. Angew. Chem. Int. Ed. 55(49), 15382 (2016) [4] Elias, X., Liu, Q., Gimbert-Suriñach, C., Matheu, R., Mantilla-Pérez, P., Martínez-Otero, A., Sala, X., Martorell, J., Llobet, A. ACS Catal. 6, 3310 (2016)

57

PS16. Covalent Organic Frameworks with Manganese Carbonyl Species for CO2 Reduction.

G.C. Dubed, 1 S. S. Mondal,1 F.Franco, 1 A. Shafir,1,* J. Lloret-Fillol1,2,* 1 Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Avinguda

Països Catalans 16, 43007 Tarragona, Spain, gdubed@iciq.es, jlloret@iciq.es 2 Catalan Institution for Research and Advances Studies (ICREA), Passeig Lluïs Companys 23, 08010 Barcelona,

Spain Effective large-scale CO2 conversion to fuels or value-added chemicals is a critical goal to reduce our impact in the environment, and helping to overcome some of the energy crisis problems [1]. Covalent Organic Frameworks (COFs) represent nowadays an interesting alternative to the more classical catalysts, with emergent properties as crystalline porous frames than potentially combine the advantages of the molecular catalysts and the heterogeneous ones [2]. In this work, we present different COFs based on tercarbonyl polypyridyl Mn units anchored to a MWCNTs via π-π stacking to form active electrocatalytic electrodes for conversion of CO2 to CO. The activity of these catalysts were evaluated by electrochemical techniques (CV, CPE) and performing high selectivity and stability in aqueous solution. Operando UV-vis spectroelectrochemistry has provided information about the formation of an intermediate during catalysis, assigned to a Mn-Mn dimeric species [3, 4]. With these materials we have integrated the Mn(bpy)CO3Br catalyst into a heterogeneous material which clearly enhances the catalytic activity with good CO2 selectivity (FE~50%) at extraordinary low overpotentials (~300 mV) in pure H2O. The first COFs frameworks based on polypyridyl tricarbonyl Mn units active for electrocatalytic CO2 reduction to CO in pure water (pH~7) were studied.

References [1] A. Sinopoli, N. T. La Porte, M. Sohail. Coordination Chemistry Reviews, 2018, 365, 60–74. [2] S. Lin, C. S. Diercks, O. M. Yaghi, Science, 2015, 349, 1208-1213. [3] B. Reuillard, K. H. Ly, E. Reisner. J. Am. Chem Soc., 2017, 169, 14425-14435. [4] M. Bourrez, M. Orio, A.Deronzier. Angew. Chem. Int., 2014, 53, 240 –243.

58

PS17. Development of new P,S-ligands for Pd-catalyzed asymmetric allylic substitution. Theoretically guided ligand optimization.

J. Saltó,1 M. Biosca,1 J. Margalef,1 X. Caldentey,2 M. Besora,2 C.Rodríguez-Escrich,2 X. C. Cambeiro,2 F. Maseras,2,3 O. Pàmies,1 M. Diéguez,1 M. A.

Pericàs2.4 1 Departament de Química Física I Inorgànica, Universitat Rovira i Virgili, C/Marcel·lí Domingo, 1, 43007

Tarragona, Spain 2 Institute of Chemical Research of Catalonia (ICIQ). The Barcelona Institute of Science and Technology, Av.

Països Catalans, 16 43007, Tarragona, Spain, 3. Departament de Química, Universitat Autònoma de Barcelona. 08193 Bellaterra, Spain. 4 Departament de Química Inorgànica i Orgànica, Universitat de Barcelona, 08028 Barcelona, Spain. Allylic substitution reaction has become a valuable tool for organic synthetic chemistry. However, most of the reported studies have shown low reaction rates, high substrate specificity and low nucleophile scope. [1] The introduction of ligands containing a phosphite-biaryl moiety have shown to be advantageous and have overcomed these limitations.[2] P,S ligands impact on allylic substitution has been limited due to the fact that high enantioselectivities were only achieved by using the standard substrates and nucleophiles.[3] In this work, we give a new push to the study of catalytic potential of P,S-ligands, including a detailed study of the catalytic species. The library was synthesized in only three steps from inexpensive indene. DFT calculations enabled the tunning and optimitzation of the ligands which were applied on a widely range of C-, N-, O-nucleophiles (40 compounds in total). Moreover, NMR studies were a key to establish the origin of the enantioselectivity. The resulting products have been derivatized by ring-clossing metathesis or Pauson-Khand reactions to prove the synthetic applicatibility and versatility of this metodology for preparing enantiopure complex structures. References [1] B. Trost, D. L. van Vranken, Chem. Rev, 1996, 96, 395-422, [2] a) Y. Mata, O. Pàmies, M. Diéguez, Adv. Synth. Catal., 2009, 351, 3217-3234; b) M. Coll, O. Pàmies, M. Diéguez, Org. Lett., 2014, 16, 1892-1895. c) O. Pàmies, M. Diéguez, Chem. Rec., 2016, 16, 2460-2481. [3] a) R. G. Arrayás, J. C. Carretero, Chem. Commun. 2011, 47, 2207-2211; b) M. Mellah, A. Voituriez, E. Schulz. Chem. Rev. 2007, 107, 5133-5209. Acknowledgements We gratefully acknowledge financial support from the Spanish Ministry of Economy and Competitiveness (CTQ2016-74878-P), European Regional Development Fund (AEI/FEDER, UE), the Catalan Government (2017SGR1472), and the ICREA Foundation (ICREA Academia award to M.D). J. S. thanks MINECO for a fellowship.

59

PS18. Catalytic Alkane Functionalization Via Iron-Carbene Insertion Reaction

Alberto Hernán-Gómez,1 Miquel Costas1 1 Institut de Química Computacional i Catàlisi, IQCC and Departament de Química, Universitat de Girona Campus

de Montilivi, 17003 Girona (Spain) e-mail: alberto.hernangomez@udg.edu.

Saturated hydrocarbons are nature abundant reagents which upon functionalization constitute a potential vast and low cost feedstock for the synthesis of more valuable chemicals.[1] However, conversion of Csp3-H into new C-C bonds is a difficult challenge due to their kinetically inert nature. To overcome this lack of reactivity, highly reactive reagents (superacids or radicals) or forcing reaction conditions are required, albeit these approaches usually compromise the selectivity of the process. An alternative to this energetically demanding processes has emerged within the field of Metal-carbene compounds LM=CR2,[2] although it is dominated by precious metals such as rhodium, silver and gold. In replacing these systems by earth-abundant metals, iron rises as an optimal choice since it is of low cost, high natural abundance and low toxicity.[3]

Herein we report our findings investigating the use of a low-valent iron organometallic species as catalysts for Csp3-H carbene insertion reactions under mild conditions. Optimization of the reaction conditions highlights the role of Lewis acids additives as a source of selectivity. Attempts to identify operative intermediates in these intricate processes are also discussed.

References

[1] R. G. Bergman, Nature 2007, 446, 391. [2] M. M. Díaz-Requejo, A. Caballero, M. R. Fructos, P. J. Pérez, Alkane C- H Activation by Single-Site Metal Catalysis, Springer, Amsterdam, 2012, Chap.6. [3] a) A. Conde, G. Sabenya, M. Rodríguez, V. Postils, J. M. Luis, M. M. Díaz-Requejo, M. Costas, P. J. Pérez, Angew. Chem. Int. Ed., 2016, 55, 6530; b) J. R. Griffin, C. I. Wendell, J. A. Garwin, M. C. White, J. Am. Chem. Soc., 2017, 139, 13624.

60

PS19. Iron Catalyzed Selective Syn-dihydroxylation of Alkenes. Catalyst Design and Elucidation of High Valent Reaction Intermediates

M. Borrell,1 E. Andris, 2 J. Roithová 2 and M. Costas.1 1Institut de Química Computacional i Catàlisi (IQCC) and Departament de Química, Universitat de Girona, Campus Montilivi, Girona E-17071, Catalonia, Spain e-mail: margarida.borrell@udg.edu. 2 Department of Organic Chemistry, Faculty of Science, Charles University, Hlavova 2030/8, 12843 Prague 2, Czech Republic Product release is the rate determining step in the arene syn-dihydroxylation reaction taking place at Rieske oxygenase enzymes, and is envisioned as a difficult problem to be resolved in the design of iron catalysts for olefin cis-dihydroxylation with potential utility in organic synthesis.[1,2] Herein a novel catalyst bearing a sterically encumbered tetradentate ligand based in the tpa (tpa = tris-(2-methylpyridyl)amine scaffold, [FeII(CF3SO3)2(5-tips3tpa)], 1 has been designed.[3,4] The steric demand of the ligand was envisioned as a key element to support a high catalytic activity by isolating the metal center, preventing bimolecular decomposition paths, and facilitating product release. In synergistic combination with a Lewis acid that helps sequestering the product, 1 provides good to excellent yields of syndiol products (up to 97% isolated yield), in short reaction times under mild experimental conditions using a slight excess of aqueous hydrogen peroxide, from the oxidation of a broad range of olefins. Predictable site selective syn-dihydroxylation of diolefins is shown. The encumbered nature of the ligand also provides a unique tool that has been used in combination with isotopic analysis to define the nature of the active species and the mechanism of O-O lysis. Gas-phase IR spectroscopy has been used to generate and spectroscopically characterize transient FeV(O) species responsible for the reaction.

References [1] Y. Feng, C.-y. Ke, G. Xue, Jr. L. Que., Chem. Commun. 2009, 50. [2] K. Chen.; Que Jr., L., Angew. Chem. Int. Ed., 1999, 38, 2227. [3] M. Borrell, M. Costas,M, J. Am. Chem. Soc. 2017, 36, 12821-12829 [4] M. Borrell, M. Costas,M, ACS sustainable Chem. Eng. 2018, 6, 8410-8416

61

PS20. After the O-O bond formation in Ru catalyzed WO: a missing link.

C.Casadevall1, V. M. Diaconescu1, W. R. Browne3, F. Franco1, N. Cabello1, J. B. Buchholz1, and J. Lloret-Fillol1,2,*

1 Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Avinguda Països Catalans, 16, 43007, Tarragona (Spain). ccasadevall@iciq.es; jlloret@iciq.es

2Catalan Institution for Research and Advanced Studies (ICREA), Lluïs Companys, 23, 08010, Barcelona, Spain

The application of artificial photosynthesis to store solar energy into chemical bonds is one of the major challenges of our society, as it offers the promise of renewable energy production [1]. Furthermore water is the most attractive source of electrons for large scale processes due to its abundance and non-toxic oxidation products (O2). However, water oxidation (WO) has been identified as the bottleneck, as it requires very high redox potentials. Therefore, to design more efficient and robust WO catalysts (WOCs) it is necessary to fully understand the intermediates involved in the O-O bond formation steps.

Figure 1. Intermediates involved in the proposed WO catalytic cycle for complex 1.

We recently reported a mechanistic study of a Ru-WOC (1) based on an aminopyridyl ligand [2], which pointed towards a high valent [RuV=O]3+ as the active species. DFT studies showed that after the O-O bond formation a [RuIII-OOH]2+ is formed, followed by a PCET yielding a singlet 2-[RuIV-OO]2+ intermediate and finally release O2. Although there have been extended discussions about the electronic nature of such postulated peroxo species, they have yet to be isolated and fully characterized [3]. Herein we report the isolation and characterization of this elusive 2-[RuIV-OO]2+ intermediate under catalytic conditions: a missing link after O-O bond formation. Characterization of 2-[RuIV-OO]2+ by X-ray, XAS, NMR, IR, HRMS and DFT shows a closed-shell heptacoordinated structure with a side-on coordination of the peroxo moiety. References [1] N. Lewis, D. G. Nocera, PNAS. 2006, 103, 15729; T. Moore et. al., Acc. Chem. Res. 2009, 42, 1890. [2] C. Casadevall, Z. Codolà, M. Costas, J. Lloret-Fillol, Chem. Eur. J. 2016, 22, 10111. [3] J. J. Concepcion et. al., JACS. 2010, 132, 1545; E. Garand et. al., ACIE. 2016, 55, 4079

62

PS21. A Stereoselective Domino Approach towards α,β-Unsaturated γ-Lactams

Jianing Xie,a Sijing Xue,a Arjan W. Kleij*,a,b 1 Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av.

Països Catalans 16, 43007 Tarragona, Spain, e-mail: xjianingi@iciq.es 2 Catalan Institute of Research and Advanced Studies (ICREA), Pg. Lluís Companys 23, 08010 Barcelona, Spain.

Small nitrogen-containing heterocycles are often found in important chemicals such as natural products, pharmaceuticals and agrochemicals. Palladium-catalyzed nucleophilic amination of allylic species represents one of the most efficient ways for the construction of new C‒N bonds. Direct amination of allylic alcohols (with OH as a challenging leaving group) using intermolecular activation has been developed as a green and atom-economical process with water as the sole by-product.[1] Despite notable progress in this area, direct aminolysis of allylic alcohols toward the stereoselective preparation of multisubstituted allylic amines still presents a fundamental and practical challenge.

Inspired by previous research in our group concerning the stereoselective formation of (Z)-configured allylic products obtained from vinyl-substituted cyclic carbonates,[2] herein we describe a new and attractive method for the amination of allylic alcohols under high stereocontrol (Figure 1). Key to this stereoselective transformation is the presence of a carboxylic acid acting as a directing and activating group. The developed catalytic process features high stereo-induction, mild reaction conditions (rt, open to air) without the need for any additives, and broad product scope producing only H2O as by-product. The isolated α,β-unsaturated lactams represent useful heterocyclic scaffolds with synthetic potential towards the formation of bioactive compounds.

References [1] a) B. Sundararaju, M. Achard and C. Bruneau, Chem. Soc. Rev., 2012, 41, 4467; b) N. A. Butt, W. Zhang,

Chem. Soc. Rev. 2015, 44, 7929. [2] a) W. Guo, L. Martínez-Rodríguez, E. Martin, E. C. Escudero-Adán, A. W. Kleij, Angew. Chem. Int. Ed., 2016,

55, 11037; b) W. Guo, L. Martínez-Rodríguez, R. Kuniyil, E. Martin, E. C. Escudero-Adán, F. Maseras, A. W. Kleij, J. Am. Chem. Soc. 2016, 138, 11970; c) W. Guo, R. Kuniyil, J. E. Gómez, F. Maseras, A. W. Kleij, J. Am. Chem. Soc. 2018, 140, 3981-3987.

63

PS22. Computational studies on phosphane-stabilized Rh and Ru nanoclusters: structure and reactivity.

A. Salom-Català1, J.J. Carbó1, J.M. Ricart Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Campus Sescelades, Marcel·lí Domingo

1, 43007 Tarragona, Spain. E-mail:antoni.salom@urv.cat

Metal nanoparticles with diameter from 1 to 10 nm (nanoclusters) have aroused great interest since their discovery because of the many of applications including catalysis.[1] The presence of organic ligands on the nanocluster surface play an important role on the control of their size and shape, however their influence on stability and reactivity of nanoclusters is not well-understood yet. Herein, we present a periodic Density Functional Theory (DFT) study on Rh and Ru nanoparticles stabilized by different types of phosphane ligands. The goal is to identify the preferred adsorption sites on nanoparticle surface as well as analyzing the nature of the phosphane interaction mode and its influence in nanoparticle structure. These nanoparticle-ligand interaction includes coordination through phosphorus lone pair and through aryl substituents of the phosphorus. Moreover, we seek to understand the reactivity of phaphanes when interaction with nanoparticles sine C-H bond activation of aryl groups was observed expermentally.[2] Interestingly, the C-H bond activation is selective depending of the phosphine type.

References [1] Nanoparticles. From theory to application, ed G. Schimd, Wiley-VCH, Weinheim, Germany, 2nd edn, 2010. [2] E. Bresó-Femenia, C. Godard, C. Claver, B. Chaudret and S. Castillón, Chem. Commun., 2015, 51, 16342-16345

64

PS23. Comprehensive computational study of redox-driven Wittig catalysis

M. Fianchini1, F. Maseras1,2 1Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Avgda.

Països Catalans, 16, 43007 Tarragona, Catalonia, Spain, mfianchini@iciq.es 2Universitat Autonoma de Barcelona, Department de Quimica, 08193 Bellaterra, Catalonia, Spain

Wittig reaction is one of the simplest and cheapest way to achieve versatile olefinic blocks1. Catalytic Wittig Reaction (CWR) belongs to the family of the redox-driven phosphorus reactions, where the phosphine oxide is recycled in situ by the means of a silane reagent. 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 (e.g. pure Z-olefins from stabilized ylides). 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). This paper presents to the audience state-of-the-art approaches in modern computation (free energy surfaces built at M06-2X-D3/def2-TZVP level with SMD solvation in toluene at 373.15 K4 complemented by kinetic models) aiming to shed definitive light on the reactivity of stabilized phosphorus ylides and to uncover the catalytic motifs behind E/Z-diasteroselective experimental 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

65

PS24. Copper(I)-catalyzed borylative cyclization towards bioactive carbocyclic compounds

J. Royes,[a] S. Ni,[b] A.Farré,[a] E. Lacascia,[a] J. J. Carbó,[a] A. B. Cuenca,*[a,c] F. Maseras,*[b] E. Fernández*[a]

[a] Dept. Química Física i Inorganica, University Rovira i Virgili, 43007-Tarragona, (Spain). [b] Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Avda Països

Catalans, 43007, Tarragona (Spain). [a, c ] Dept. Organic and Pharmaceutical Chemistry, Institut Química Sarrià, University Ramón Llull, 08017 Barcelona

(Spain). e-mail: jordi.royes@urv.cat Borylative cyclizations of alkenes in the presence of appropriate leaving groups allow for the

selective synthesis of target organoboron compounds with remarkable bioactivity.[1,2]

Inspired by the efficient borylative exo-cyclization of alkenyl halides reported by Ito et al.,[3]

we have complemented the study focusing on the synthesis of boron-containing spiro

compounds. Our work hypothesis is based on the regioselective addition of a borylcopper(I)

specie to unactivated terminal alkenes, locating the C-Cu bond in the internal position.

Interestingly, the new alkylcopper(I) specie efficiently reacts intramolecularly with the

alkylhalide to generate a new C-C bond providing a cyclic system with a borylmethyl moiety

that could be further functionalize.[4]

In order to have deeper insights about the mechanism and the corresponding formation of

these novel spiro compounds, DFT calculations were carried out to support the experimental

results.[5]

References: [1] Kubota, K.; Iwamoto, H.; Ito, H.Org. Biomol. Chem. 2017, 285 [2] Bunuel, E.; Cardenas, D. J. Eur. J. Org. Chem. 2016, 5446 [3] Kubota, K.; Yamamoto, E.; Ito, H. J. Am. Chem. Soc. 2013, 2635 [4] E. La Cascia, A. B. Cuenca, E. Fernandez, Chem. Eur. J. 2016, 22, 18737. [5] J. Jover, F. Maseras, Organometallics 2016, 35, 3221.

66

PS25. Metal-ligand Cooperative Catalysis with Indene based Pd and Pt Pincer Complexes

B. Martin Vaca, J. Monot, D Bourissou 1 LHFA, Université Paul Sabatier, 118 Route de Narbonne, 31062 Toulouse, FRANCE bmv@chimie.ups-tlse.fr

Over the past two decades, spectacular progress has been achieved in the field of Metal/Ligand cooperative catalysis using pincer complexes. In particular, Milstein discovered an original aromatization/dearomatization process in pyridine-based pincer complexes that has been applied to a wide range of efficient transformations [1].

We have described original indenediide Pd(II) and Pt(II) pincer complexes combining an electrophilic metal center and an electron-rich ligand backbone [2]. This indenediide pincer ligand shows a non-innocent behavior that has been applied in the catalytic intramolecular addition of carboxylic acids/amides to alkynes in the absence of external base. An important breakthrough was obtained for the formation of 5-, 6- and even 7-membered ring lactones/lactams including the first efficient preparation of -

methylene caprolactones/lactams [3]. A remarkable behavior has also been evidenced in the construction of the oxazolididone motif from propargylamines using CO2 as C1 building block. The results show that the indenediide Pd(II) pincer complexes perform very efficiently, with a broad scope of substrates in terms of alkyne substitution and class of amine [4]. We are currently seeking to expand the applications of these complexes to other valuable transformations, in particular cyclizations involving C-C bond creation. All these aspects will be illustrated in the poste. References [1] C.Gunanathan, D. Milstein, Acc. Chem. Res. 2015, 48, 1979. [2] N. Nebra, J. Lisena, N. Saffon, L. Maron, B. Martin-Vaca, D. Bourissou, Dalton Trans. 2011, 40, 8912. [3] (a) N. Nebra, J. Monot, R. Shaw, B. Martin-Vaca, D. Bourissou, ACS Catal. 2013, 3, 2930; (b) N. A. Espinosa-Jalapa, D. Ke, N. Nebra, L. Le Goanvic, S. Mallet-Ladeira, J. Monot, B. Martin-Vaca, D. Bourissou, ACS Catal. 2014, 4, 3605. (c) J. Monot, P. Brunel, C. E. Kefalidis, N. A. Espinosa-Jalapa, L. Maron, B. Martin-Vaca, D. Bourissou, Chem. Sci. 2016, 7, 2179. [4] P. Brunel, J. Monot, C. E. Kefalidis, N. A. Espinosa-Jalapa, L. Maron, B. Martin-Vaca, D. Bourissou ACS Catal, 2017, 7, 2652.

67

PS26. Organo-Catalyzed Ring-Opening Reaction of epoxides with gem-Diborylalkanes. R. Gava, E. Fernández

Departamento de Química Física e Inorgánica,University Rovira i Virgili, C / Marcel·lí Domingo S/N Edificio N4 Campus Sescelades 43007 Tarragona.

The borylative ring-opening of vinylepoxides with the adduct [MeO→Bpin-Bpin]- (Bpin = pinacolboryl) has been described in our group in recent years.[1] The reactivty was described as a SN2’ nucleophilic attack of the Bpin unit to the conjugated vinylepoxides. Now we focussed our efforts to develop a nucleophilic attack of the carbanion formed from the geminal diboron reagent (bis(pinacolato)borylmethane) and LiTMP,[2] into the vinylepoxides, providing a direct ring opening reaction and keeping the double bond unaltered. This new reaction provides beneficial applications for further functionalization of the resulting homoallylic gem-diboronated compounds.

References [1] X. Sanz, G. M. Lee, C. Pubill-Ulldemolins, A. Bonet, H. Gulyás, S. A. Westcott, C. Bo, E. Fernández, Org. Biomol. Chem. 2013, 11, 7004. [2] N. Miralles, R. J. Maza, E. Fernández, Adv. Synth. Catal. 2018, 360, 1306.

68

PS27.A Novel 1,4-Hydroboration reaction with 1,3-dienes. An experimental and theoretical point of view.

Ricardo J. Maza, Jordi J. Carbó, E. Fernández Dept. Química Física e Inorgánica, University Rovira I Virgili, C/Marcelí Domingo s/n, Tarragona, Spain.

E-mail: ricardojose.maza@urv.cat; mariaelena.fernandez@urv.cat; j.carbo@urv.cat; Tel +34 977 558285

In the present work, the synthesis of versatile organoboron compounds from 1,3-diene substrates in a transition metal-free context is outlined. The work focuses on optimizing the base-catalysed addition of diboron compounds to 1,3-dienes through 1,4-hydroboration. At the same time, a computational study is also carried out to understand the reaction mechanism and selectivity in the aforementioned synthesis.

This 1,4-hydroboration of 1,3-dienes takes advantage of the interesting reactivity displayed by the Lewis acid-base adduct formed between diboron compounds and the methoxide anion. This form of catalysis is transition metal-free, utilizing only a base which activates the diboron compound (bis(pinacolato)diboron) in a protic medium such as methanol. The base abstracts a proton from the methanol to form a methoxide anion, which forms a Lewis acid-base adduct with the diboron compound. Upon coordination of the methoxide, the -bonding orbital of the B-B bond becomes polarized towards sp2 boron via “push-pull” efect, gaining an important nucleophilic character being able to attack electrophilic centers [1,2].

References [1] J. Cid, H. Gulyás, J. J. Carbó, E. Fernández, Chem. Soc. Rev. 2012, 3558-3570. [2] A. B. Cuenca, H. Shihido, H. Ito, E. Fernández, Chem. Soc. Rrev. 2017, 415-130.

69

PS28. -Lactone Production in Two-Phase Catalysis with In-Situ Extraction

M. Y. Souleymanou1, C. Godard1, A. M. Masdeu-Bultó1, G. Francio2, W. Leitner3 1 Department of Physical and Inorganic Chemistry, University Rovira I Virgili, Tarragona (Spain) 2 Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Aachen (Germany) 3 Max-Planck Institute for Chemical Energy Conversion, Mulheim (Germany) Corresponding author: myriam.souleymanou@urv.cat

Homogeneous catalysts offer numerous advantages over their heterogeneous counterparts. For example, the steric and electronic properties of the catalyst can be controlled by tuning the metal atom and ligands therefore, high activities and selectivies can be achieved. Furthermore, the solubility of the catalyst constitutes an important asset in terms of catalysts site availability. However, its solubility constitutes the major drawback in terms of catalyst separation and reuse.[1] Thus, the quests for new catalyst immobilization or recovery strategies to facilitate its recycling are of utmost importance. In line of this, biphasic catalysis represents an attractive approach as it combines the advantages of homogeneous catalysis with easy catalyst recycling.[2] In this contribution, our investigation on the telomerization reaction of 1,3 butadiene with carbon dioxide (CO2) in a biphasic catalytic system consisting of environmentally benign reaction media ionic liquid (IL) and supercritical CO2 (ScCO2) is presented. We also demonstrate that scCO2 can be employed for facile δ-lactone product extraction without cross contamination by IL and/or catalyst, thus allowing catalyst efficient recycling. References

[1] L. Can, L. Yan, Bridging Heterogeneous and Homogeneous Catalysis: Concepts, Strategies, and Applications, Wiley-VCH Verlag GmbH & Co. KGaA, 2014 [2] B. Cornils, W. A. Herrmann, I. T. Horváth, W. Leitner, S. Mecking, H. Olivier-Bourbigou, D. Vogt, Multiphase Homogeneous Catalysis, Wiley-VCH Verlag GmbH & Co. KGaA, 2005

70

PS29. Enantioselective Construction of Tertiary Sulfones via Copper-Catalyzed Propargylic Substitution

José Enrique Gómez,† Àlex Cristòfol,† and Arjan W. Kleij*,†,§

†Institute of Chemical Research of Catalonia (ICIQ), the Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 – Tarragona, Spain

§Catalan Institute of Research and Advanced Studies (ICREA), Pg. Lluís Companys 23, 08010 – Barcelona, Spain e-mail: jgomez@iciq.es Sulfur-containing tetrasubstituted carbon stereocenters are frequently embedded in numerous natural products, biologically active small molecules and pharmaceutical ingredients, as exemplified by Tazobactam.[1] Hence, the asymmetric construction of sulfur-containing stereocenters is of utmost importance in organic synthesis. Copper-catalyzed propargylic substitution is regarded as a direct strategy towards the enantioselective construction of substrates leading to quaternary centers.[2] Whereas remarkable progress has been achieved with a relatively wide range of nucleophiles, to the best of our knowledge S-nucleophiles have not been yet explored in an asymmetric context. Herein, we communicate the first asymmetric synthesis of important propargylic sulfones featuring tetrasubstituted tertiary carbons, via Cu-catalyzed propargylic substitution, using simple sulfinate salts as nucleophiles. This methodology features good yields and selectivities, synthetic diversity, wide product scope, and provide an approach to -hydroxysulfone motifs, which are imperative scaffolds in biologically active compounds.

S

F

HN

O

CF3

CN

OHOO

N

S

O

O O

NN

NCO2H

HO

SO

On-C13H27

OO

O

R

R1SO2Na

[Cu], BOX ligand, BaseOH

SO2R1

R

-CO2

Quaternary C-S centersHigh yield & high er'sKey building blocksPractical methodology

-hydroxysulfones

References [1] Yu, J.-S.; Huang, H.-M.; Ding, P.-G.; Hu, X.-S.; Zhou, F.; Zhou, J. ACS. Catal. 2016, 6, 5319. [2] Hu, X.-H.; Liu, Z.-T.; Shao, L.; Hu, X.-P. Synthesis, 2015, 47, 913.

71

PS30. Transforming CO2 into cyclic carbonate using lignocellulosic waste as catalyst: experimental and computational approach

M. B. Yeamin1, M. S. El Ouahabi1,2, A. Aghmiz2, M. Reguero1 and A. M. Masdeu-Bultó1

1Universitat Rovira i Virgili, Departament de Química Física i Inorgànica, C. Marcel·lí Domingo 1, 43007-Tarragona, Spain, *email: yeamin.mdbin@urv.cat

2Faculté des Sciences, University Abdelmalek Essaadi, Mhannech II, B.P. 2121, 93030 Tétouan, Morocco The world chemical industries are nowadays very much dependent on oil and gas, and there are concerns about their future availability. Valorization of carbon dioxide to high value chemicals and polymers is a fast emerging area [1,2]. Furthermore, the need of decreasing the greenhouse gas emmissions in the atmosphere made the CO2 transformation a promising research area. The main drawback is its thermodynamic stability and kinetic inertness. To overcome this problem the use of catalysts or highly reactive substrates is required. For example, epoxides react with CO2 in the presence of a catalyst to form cyclic carbonates (Scheme 1) [3].

Scheme 1. Cycloaddition of CO2 and epoxides.

We present the catalytic performance of some lignocellulosic biomass wastes such as residues from olives, sawdust, cereals and grapes in combination with nucleophiles, in the conversion of CO2 into cyclic carbonate. The mechanistic study with Density Functional Theory (DFT) provides the molecular interpretation of the catalytic process.

References [1] R. Rajagupal, Sustainable Value Creation in the Fine and Speciality Chemicals Industry, John Wiley & Sons Ltd., 2014. [2] M. Alves, B. Grignard, R. Mareau, C. Jerome, T. Tassaing, and C. Detrembleur, Catal. Sci.Technol., 2017, 7, 2651. [3] L. Cuesta-Aluja, A. Campos-Carrasco, J. Castilla, M. Reguero, A. M. Masdeu-Bultó, A. Aghmiz, J. CO2 Utilization, 2016, 14, 10.