Group of development of catalyst for industrial processes
Our hallmark is the study of organometallic chemistry at a fundamental level. However, our mission is to develop and study new catalysts that improve the sustainability of chemical industry processes. In particular, we focus on those that lead to the formation of new organic molecules with high added value, or the production of polymers. This objective has led us to focus our interest on the chemistry of the chemical elements that are most abundant in the Earth’s crust, which includes, in addition to those that make up classic organic molecules (C, H, N, O, S, etc.), the metals of the first transition series (Ti – Cu), post-transition (Zn) and s (Mg) and p (Al) blocks. Our interest is not so much focused on the optimisation of specific catalytic processes (we leave that to groups specialising in the development of synthetic methods) as on the exploration of new processes or ideas that may represent a novel contribution to the field of catalysis. We believe that it is in this field where our experience in organometallic synthesis, reactivity studies and reaction mechanism research can be most useful.
Our experience initially focused on the organometallic chemistry of transition elements, specifically those in Group 10: nickel and palladium. From there, our interest has expanded to other molecular derivatives of the first transition series (3d series: Mn, Fe, Co, etc.), as well as to the organometallic chemistry of the main group elements (mainly Zn, Mg, and Al). Our group has also made inroads into organocatalysis, i.e., the study of catalysts that do not include any heavy metals in their composition.
The methodology on which our capabilities are based is the synthesis, isolation and complete characterisation of catalysts and reaction intermediates, efficiently and with as few steps as possible. This implies lower consumption of energy, reagents and solvents. We also favour the study of those elements which, due to their abundance, can be considered sustainable resources.
Main research areas
1. Formation of polymers with well-defined molecular weight distributions. In this line of work, we focus on Ziegler-Natta catalysts. The origin of this interest lies in a collaborative project with the company Repsol, which lasted for more than a decade, with the aim of developing well-defined catalysts for the production of polyolefins (mainly polyethylene, but also, to a lesser extent, in the polymerisation of propene and butadiene). In this project, we studied catalysts based on transition elements (Ti, Zr, Fe, Co and, in particular, Ni, given our experience in this field).
2. Recently, we have become interested in the production of polyesters with very precise molecular weights through the ring-opening methodology (ROP, or ‘Ring Opening Polymerisation’) with main group complexes and also organocatalysts.
3. The replacement of the precious element Pd in its most important applications with Ni, one of the most abundant metals on our planet. Our group has focused on the study of nickel catalysts for the Heck reaction, one of the most versatile applications of homogeneous catalysis in organic synthesis, which is catalysed very specifically by palladium compounds. Our approach to the problem focuses on the application of the concept of active metal-ligand cooperation, for which the appropriate design of the latter is essential, based on a precise knowledge of the catalytic cycle. In this line of work, we take as our starting point and exploit our experience in the development of well-defined Ziegler-Natta-type molecular catalysts.
4. Likewise, our group has taken an interest in Ni and Pd alkoxide and hydroxide complexes, which catalyse reactions of great interest, such as the oxidation of ethylene to acetaldehyde (Wacker reaction) or the selective oxidation of alcohols with O2, an application of Ni and Pd complexes, a field in which our work has focused for many years and to which we have made numerous contributions.
5. The most recent line of work in our group, which is the subject of our current projects, is an example of bio-inspired catalysis: the development of catalysts for hydrogen atom transfer reactions, for which we use the function of the biological cofactor NAD+/NADH as a model. Our original approach is to use stable organometallic compounds of Al and Zn, whose metal centre acts as a modifier of an active organic structure, providing both the REDOX activity and the H transport function required by the process, thus reversing the functional relationship between the metal and the ligand. Our medium-term goal is to develop a biomimetic system that mimics the activity of the alcohol dehydrogenase enzyme, using only simple organometallic complexes. In this line of work, we are focusing on the development of the 2,6-Bis(imino)Pyridine (BIP) platform of non-innocent and redox-active ligands. The choice of this type of ligand is not accidental, as it also has its origins in our research project on Fe and Co catalysts for ethylene polymerisation, sponsored by the Repsol company.
6. Our group is also very interested in the development of a new type of dipolar molecule: NHC-CDI betaines, or adducts formed by stable heterocyclic carbenes (NHC) with carbodiimides (CDI). One of the most characteristic properties of these molecules is the internal separation of electrical charge, forming a dipole that is not cancelled out in any canonical resonance representation. Despite their relatively simple structure, these molecules were virtually unknown until our group rediscovered them in 2014, publishing the first results throughout 2015. Since then, these molecules have demonstrated their versatility, giving rise to numerous applications as ligands, for the stabilisation of nanocatalysts, as powerful nucleophilic catalysts capable of activating C-Cl bonds in dichloromethane and other organochlorines, and catalysing their conversion into high value-added products.
Pilar Palma Ramirez
Scientific Researcher
Juan Manuel Delgado Collado
PhD Student
Diego Alexandre Cabo Palacios
PhD Student
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Juan Manuel Delgado-Collado,Francisco José Fernández de Córdova, Pilar Palma, Juan Cámpora, and Antonio Rodríguez-Delgado. Turning the Tables: Ligand-Centered Hydride Shuttling in Organometallic BIP–Al Systems. Inorg. Chem., 2025, 64, 15760. DOI: 10.1021/acs.inorgchem.5c02587
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- Tomás G. Santiago, Pilar Palma, Juan Cámpora. A tale of two metals: The Mizoroki-Heck reaction as a guide to compare the chemical characters pf nickel and palladium in catalysis. Adv. Organomet. Chem., 2024, 81, 1-166
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David Sánchez-Roa, Valentina Sessini, Marta E. G. Mosquera, and Juan Cámpora. N-Heterocyclic Carbene-Carbodiimide (NHC-CDI) Betaines as Organocatalysts for β-Butyrolactone Polymerization: Synthesis of Green PHB Plasticizers with Tailored Molecular Weights ACS Catal., 2024, 14, 2487. DOI: 10.1021/acscatal.3c05357
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- López, J.A.; Cabo, D.A.; Palma, P.; Cámpora, J. A Comparison of β–Phenyl Elimination in Nickel and Palladium Alkyl Complexes: A Potentially Relevant Process in the Mizoroki–Heck Reaction. Inorganics, 2024, 12, 89. DOI: 10.3390/inorganics12030089
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- Juan Manuel Delgado-Collado, Hellen Videa, Pablo J. Serrano-Laguna, M. Ángeles Fuentes, Eleuterio Álvarez, Antonio Díaz Quintana, Antonio J. Martínez-Martínez, Antonio Rodríguez-Delgado, Juan Cámpora. Reversible Redox Ligand-Centered Reactivity in 2,6-Bisiminopyridine Aluminum Systems. Inorg. Chem., 2024, 63, 19156. DOI: 10.1021/acs.inorgchem.4c02664
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- David Sánchez-Roa, Marta E. G. Mosquera, Juan Cámpora. NHC-CDI Betaine Adducts and Their Cationic Derivatives as Catalyst Precursors for Dichloromethane Valorization J. Org. Chem., 2021, 86, 16725. DOI: 10.1021/acs.joc.1c01971
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- Luis M. Martínez-Prieto, Pilar Palma, Eleuterio Álvarez, and Juan Cámpora. Nickel Pincer Complexes with Frequent Aliphatic Alkoxo Ligands [(iPrPCP)Ni-OR] (R = Et, nBu, iPr, 2‑hydroxyethyl). An Assessment of the Hydrolytic Stability of Nickel and Palladium Alkoxides. Inorg. Chem., 2017, 56, 13086. DOI: 10.1021/acs.inorgchem.7b01868
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- Astrid Márquez, Elena Ávila, Carmen Urbaneja, Eleuterio Álvarez, Pilar Palma, and Juan Cámpora. Copper(I) Complexes of Zwitterionic Imidazolium-2-Amidinates, a Promising Class of Electroneutral, Amidinate-Type Ligands Inorg. Chem., 2015, 54, 11007. DOI: 10.1021/acs.inorgchem.5b02141
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- M. A. Cartes , A. Rodrı́guez-Delgado , P. Palma , E. Álvarez , and J. Cámpora. Sequential Reduction and Alkyl Exchange Reactions of Bis(imino)pyridine Dialkyliron(II) with Trimethylaluminum. Organometallics, 2014, 33, 1834. DOI: 10.1021/om500167r
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- L. Ortiz de la Tabla, I. Matas, P. Palma, E. Álvarez, and J. Cámpora. Nickel and Palladium Complexes with. New Phosphinito-Imine Ligands and Their Application as Ethylene Oligomerization Catalysts. Organometallics, 2012, 31, 1006. DOI: 10.1021/om201088y
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Cristóbal Melero, Luis M. Martínez-Prieto, Pilar Palma, Diego del Rio, Eleuterio Álvarez and Juan Cámpora. Selective reduction of a Pd pincer PCP complex to well-defined Pd(0) species. Chem. Commun., 2010, 46, 8851
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Catálisis con Metales Abundantes: Un Enfoque Bio-Inspirado
Project funded by: PID2024-161649NB-100
Validity: 2025-2028
Entity: Ministerio de Ciencia, Innovación y Universidades
Manipulación de ligandos en posiciones remotas para potenciar la catálisis con complejos de metales abundantes
Project PID2021-128392NB-100 funded by:
Validity: 2022-2025
Entity: Ministerio de Ciencia, Innovación y Universidades
Catálisis sin metales preciosos: Evaluación de ligandos modulares proactivos
Project P20-00104 funded by:
Validity: 2021-2023.
Entity: Junta de Andalucía. (Regional Project).
Generación de pautas cooperativas en complejos de metales no preciosos con ligandos versátiles
Project PGC2018-095768-B-l00 funded by:
Validity: 2019 – 2022.
Entity: AEI-MICINN. (Government)
Desarrollo de plataformas versátiles metal/ligando para nuevas aplicaciones en catálisis homogénea
Project CTQ2015-68978-P funded by:
Validity: 2016-2019.
Entity: DIGICIT, MINECO. (Government).
Desarrollo y estudio de nuevos catalizadores homogéneos para la transformación […]
Project CTQ2012-30962 funded by:
Validity: 2013-2015.
Entity: DIGICIT, MINECO (Government).
Catalizadores homogéneos para la producción de materiales poliolefínicos avanzados
Project P09-FQM-5074 funded by:
Validity: 2010-2014.
Entity: Junta de Andalucía (Regional Project).
Inventores: Luis Méndez, Antonio Muñoz-Escalona, Juan Cámpora, Ernesto Carmona, Manuel López Reyes
N.º de solicitud: EPO 00500040.1
País de prioridad: España
Fecha de prioridad: 13-03-2000
Entidad titular: REPSOL YPF
Países a los que se ha extendido: Austria, Bélgica, Alemania, España, Finlandia, Francia, Gran Bretaña, Italia y Holanda
Bidentate diimine nickel and palladium complexes and polymerization catalysts obtained therefrom
Inventores (p.o. de firma): Luis Méndez, Antonio Muñoz-Escalona, Juan Cámpora, Ernesto Carmona, Manuel López Reyes
N.º de solicitud: EPO 00500041.9
País de prioridad: España
Fecha de prioridad: 13-03-2000
Entidad titular: REPSOL YPF
Países a los que se ha extendido: Austria, Bélgica, Alemania, España, Finlandia, Francia, Gran Bretaña, Italia y Holanda
Catalizador para la polimerización de etileno y dienos, procedimiento de preparación y utilización
Inventores (p.o. de firma): Juan Cámpora, M. Mar Conejo, E. Carmona
N.º de solicitud: 200201622
País de prioridad: España
Fecha de prioridad: 10-07-2003
Entidad titular: CSIC
países a los que se ha extendido: Europa, Estados Unidos, Japón, Canadá
Polyethylene compositions and their use in the manufacture of pipes
Inventores (p.o. de firma): m. L. Reyes, C. Martín, O. Prieto, J. Sancho, J. Cámpora, P. Palma, A. M. Naz, C. Pérez
N.º de solicitud: EP2003166 A1
País de prioridad: Países europeos
Fecha de prioridad: 12-06-2007
Entidad titular: Repsol-YPF
Países a los que se ha extendido: Europa
Procedimiento para la oxidación de alcoholes con un catalizador homogéneo de paladio
Inventores (p.o. de firma): Juan Cámpora, Pilar Palma, Cristobal Melero, Oleg Shishilov
N.º de solicitud: P201132079
País de prioridad: España
Fecha de prioridad: 22/12/2011
Entidad titular: Consejo Superior de Investigaciones Científicas
Países a los que se ha extendido: países del convenio PCT
Trampa molecular para la captura selectiva de disulfuro de carbono y de otros compuestos tóxicos relacionados
Inventores (p.o. de firma): Juan Cámpora, Elena Ávila, Mercedes Luque, Pilar Palma
N.º de solicitud: PCT/ES2018/070693
País de prioridad: España
Fecha de prioridad: 24/10/2017
Entidad titular: Consejo Superior de Investigaciones Científicas
Países a los que se ha extendido: países del convenio PCT
Procedimiento para la obtención de acetales, ditioacetales y aminales a partir de diclorometano
Inventores (p.o. de firma): Juan Cámpora Pérez, Marta Elena González Mosquera, David Sánchez Roa
N.º de solicitud: P202130376
País de prioridad: España
Fecha de prioridad: 28/04/2021
Entidad titular: Consejo Superior de Investigaciones Científicas y Universidad de Alcalá de Henares
Composite biomaterials for 3D printing of medical devices
Inventores: Norge Cruz Hernández, Antonio Rodríguez Delgado, Ramón González
N.º de solicitud ES2674178A1, 169:140848 (WO)
País de prioridad: todos los del mundo
Fecha de prioridad: 2018
Entidad Titular: Universidad de Sevilla