The primary aim of our research team is to synthesize organometallic molecules with specific electronic and steric properties enabling the activation and functionalization of different types of bonds. We are interested in developing new efficient catalysts, with an important effort in the understanding of the mechanisms by which the metal complexes operate. Also, we focus on fundamental aspects elucidating the detailed electronic structure and reactivity patterns of the organometallic molecules. As such, our research program spans the areas of organic synthesis, catalysis, and organometallic chemistry. Currently, some of our research programs deal with group 10 transition metals (mainly nickel and platinum) stabilized by pincer bis(phosphino)boryl and N-heterocyclic carbene ligands and exploring their potential in small molecule activation and dehydrocoupling processes leading to B-N, Si-N, C-Si and C-B bonds. Another research topic in our group focuses on multinuclear group 11 metal-containing complexes (gold and copper) supported by NHC ligands, and the investigation of novel reactivity modes.
Main research lines
1.Low-electron count platinum complexes stabilized by N-heterocyclic carbenes
During the last years we have been involved in the isolation of stable, yet reactive, cationic Pt(II) 14-electron species making use of the excellent stereoelectronic properties of N-heterocyclic carbene ligands. The reactivity of these compounds has allowed to synthesize unusual platinum complexes in the oxidation states +3 and +4.
14-electron Pt(II) complexes interact with dihydrogen, hydroboranes, hydrosilanes and hydrogermanes to form σ-complexes that can undergo further reactivity in catalytic reactions. We have observed that these catalytic processes involve outer-sphere mechanisms in which boronium- and silylium like cations are involved, allowing the catalytic construction of B-N, Si-N, Si-O and Si-C bonds.
2. Bis(phosphino)boryl nickel catalysts for small molecules activation
Our group is currently focused on nickel-catalyzed transformations and fundamental mechanistic studies, using bis(phosphino)boryl nickel systems. The reactivity of the nickel-boryl unit in these systems is characterized by three key features: i) the strong trans influence exerted by the boryl group; ii) the amphiphilic character of the boron center; iii) the nickel-boryl cooperative reactivity. Building on these electronic properties, our group has investigated different catalytic or stoichiometric reactions that take advantage on these characteristics. Shown above are examples that demonstrate the versatility of our systems, ranging from catalytic reduction of carbon dioxide to aldehydes, to the borylation of alkenes or the activation of small molecules like hydrogen or ammonia.
- Electron-rich digold acetylide complexes
Over the past decade, there has been an increased interest in the role of two gold(I) atoms in the homogeneous catalytic transformation of organic substrates containing π-systems, and bimetallic gold(I) catalysis has enabled the synthesis of organic compounds that were previously inaccessible. This productivity derives from the electrophilic activation that π substrates undergo upon coordination to unsaturated gold species, namely π-activation or σ,π-activation. In our group, we are currently focusing on the role that unexplored σ,σ-bound species play in the activation of different substrates. For instance, we have recently observed that two gold(I) fragments provide enough electron density to a triple bond to activate electron deficient alkynes or small molecules such as CS2, leading to their formal insertion in Au−C bonds. In comparison, monometallic analogues are not able to achieve such transformation, or they require much more extreme experimental conditions.
4. Molecular electrocatalysis
When thinking about molecular electrocatalysis, one can inadvertently fall into the analogy of homogeneous catalysis. However, electrocatalysis has an unparalleled advantage over homogeneous (thermal) catalysis, as it is capable (in principle) of reducing the energy required for these reactions to occur. In the context of the urgent need to decarbonise our energy systems and progress toward carbon neutrality, advancing energy-efficient catalytic processes is essential. A prime example lies in energy storage and conversion via chemical bonds, such as green hydrogen production, carbon and nitrogen-based energy cycles, and the electrification of chemical synthesis. Our research focuses on the electrochemical reduction of carbon dioxide (eRRCO2), with plans to expand to other cathodic processes, including the oxygen reduction reaction (eORR) and the hydrogen evolution reaction (HER). To this end, we have developed a suite of multidentate ligands designed to coordinate mono-, bi-, and multimetallic complexes using only first-row transition metals (Fe, Ni, Co, Cu). These molecular electrocatalysts are engineered to facilitate both single- and multi-electron transfers through cooperative metal–metal and metal–ligand interactions, including proton shuttling mechanisms. Our work encompasses: A) Synthesis and characterisation of ligands and metal complexes; B) Electrochemical and electrocatalytic evaluation via cyclic voltammetry, rotating disk/ring-disk electrodes, and preparative electrolysis; C) In situ spectroelectrochemical studies to probe catalytic mechanisms and identify reaction intermediates; D) Isolation and characterisation of active species.
- I. Nieto-Vargas, J. Cayuela-Castillo, F. J. Fernández-de-Córdova, I. Fernández, P. Ríos, Haptotropic phenomena in digold(I) triple-bonded complexes, 2025, ChemRxiv, https://doi.org/10.26434/chemrxiv-2025-63h9j
- Cayuela-Castillo, F. J. Fernández-de-Córdova, M. S. See, I. Fernández, P. Ríos, Stepwise alkyne insertion in Au(I) acetylides: influence of the nuclearity, Chem. Sci. 2025, 16, 4684-4694. This article is part of the themed collection 2025 Chemical Science HOT Article Collection.
- J. Laglera-Gándara, R.l Jiménez-Rioboó, L. Álvarez-Rodríguez, R. Peloso, P.o Ríos, A. Rodríguez Nickel-Catalyzed Deuteration of Primary, Secondary, and Tertiary Silanes: Scope and Mechanistic Insights J. Org. Chem. 2025, DOI: 10.1021/acs.joc.5c00107.
- J. Laglera-Gándara, J. Jiménez-Pérez, F. J. Fernández-de-Córdova, P. Ríos, S. Conejero, Electrophilic Hydrosilylation of Electron-Rich Alkenes Derived from Enamines, Angew. Chem. Int. Ed. 2024, 63, e20240485. DOI: 10.1002/anie.202404859
- Álvarez-Rodríguez, P. Ríos, C. J. Laglera-Gándara, A. Jurado, F. J. Fernández de Córdova, T. B. Gunnoe, A. Rodríguez, Cleavage of Carbon Dioxide C=O Bond Promoted by Nickel-Boron Cooperativity in a PBP-Ni Complex, Angew. Chem. Int. Ed. 2023, 62, e202306315. DOI: https://doi.org/10.1002/anie.202306315
- Kong, P. Ríos, C. Hauck, F. J. Fernández de Córdova, D. A. Dickie, L. G. Habgood, A. Rodríguez, T. B. Gunnoe, Ethylene dimerization and oligomerization using bis(phosphino)boryl supported Ni Complexes, J. Am. Chem. Soc. 2023, 145, 179-193. DOI: https://doi.org/10.1021/jacs.2c09471
- Fouilloux, M.-N. Rager, P. Ríos, S. Conejero, C. M. Thomas, Highly Efficient Synthesis of Poly(silylether)s: Access to Degradable Polymers from Renewable Resources, Angew Chem. Int. Ed. 2022, 61, e202113443. Selected as Very Important Paper DOI: https://doi.org/10.1002/anie.202113443
- Ríos, F. J. Fernández-de-Córdova, J. Borge, G. Sciortino, A. Lledós, A. Rodríguez, Ambiphilic Boryl Groups in a Neutral Ni(II) Complex: A New Activation Mode of H2, Chem. Sci. 2021, 12, 2540. DOI: https://doi.org/10.1039/D0SC05522K
- Ríos, R. Martín de la Calle, P. Vidossich, F. J. Fernández de Córdova, A. Lledós, S. Conejero, Reversible carbon–boron bond formation at platinum centers through σ-BH complexes Chem. Sci. 2021, 12, 1647-1655. Selected as Pick of the Week and Front Cover DOI: https://doi.org/10.1039/D0SC05522K
- Ríos, H. Fouilloux, P. Vidossich, J. Díez, A.Lledós, S. Conejero, Isolation of a Cationic Pt(II) σ-Silane Complex Angew. Chem. Int. Ed. 2018, 57, 3217-3221. DOI: https://doi.org/10.1002/anie.201712791
- Samantha L. Peralta-Arriaga,” Miguel Angel Martín-Neri,” Carlos García Bellido, Jeremy De Freitas, Sukanta Saha, Francisco José Fernández-de-Córdova, Marc Robert, Orestes Rivada Wheelaghan.* Access to heterobimetallic MII/CuI complexes with a multichelate platform and their reactivity studies in CO2RR. Inorg. Chem. 2025, 64, 4835-4843. https://pubs.acs.org/doi/full/10.1021/acs.inorgchem.4c04471
- Carlos Martínez-Ceberio, Francisco José Fernández–de–Córdova, Orestes Rivada-Wheelaghan*. Synthesis and Characterization of Bimetallic Copper (I) Complexes Supported by a Hexadentate Naphthyridine-Based Macrocycle Ligand. Inorg. Chem. 2025, 64, 8630-8638. https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00321
- Antoine Bohn, Juan José Moreno, Pierre Thuéry, Marc Robert, Orestes Rivada–Wheelaghan*. Electrocatalytic CO2 reduction with a binuclear bis-terpyridine pyrazole-bridged cobalt complex. Chem. Eur. J. 2023, 29, e202202361. (Invitation 2022 Young Chemists Special Collection). https://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/chem.202202361
- Daniela Mendoza, Si-Thanh Dong, Nikolaos Kostopoulos, Victor Pinty, Orestes Rivada-Wheelaghan, Elodie Anxolabéhère-Mallart, Marc Robert, Benedikt Lassalle-Kaiser. In situ X-ray absorption spectroscopy in homogeneous conditions reveals interactions between CO2 and a doubly and triply reduced iron(III) porphyrin, then leading to catalysis. ChemCatChem 2023, 15, e202201298. https://chemistry-europe.onlinelibrary.wiley.com/toc/18673899/2023/15/7
Cooperatividad entre Metales de Transición-Elementos Principales y Efectos de los Ligandos en Catálisis
Project PID2022-141925NB-I00 funded by:
Project: PID2022-141925NB-I00
Entity: Ministerio de Ciencia, Innovación y Universidades
Validity: 01.09.2023 – 31.08.2026
Estructura y reactividad de complejos metálicos derivados de la activación de silanos y boranos
Project PID2019-109312GB-I00 funded by:
Project: PID2019-109312GB-I00
Entity: Ministerio de Ciencia, Innovación y Universidades
Validity: 01.06.2020-31.05.2023
Complejos de Cobre Altamente Reactivos: Síntesis, Reactividad y Propiedades Fotoluminiscentes
Project ProyExcel_00758 funded by:
Project: ProyExcel_00758
Entity: Junta de Andalucía
Validity: 02.12.2022-31.12.2025
Explorando Nuevos Modos de Reactividad con Complejos de Níquel y Platino
Project P20_00513 funded by:
Project: P20_00513
Entity: Junta de Andalucía
Validity: 01.06.2020-30.06.2023
Complejos acetiluro de oro de alta valencia: síntesis y reactividad
Project PID2024-160351NA-I00 funded by:
Project: PID2024-160351NA-I00
Entity: Ministerio de Ciencia, Innovación y Universidades
Validity: 01.09.2025-31.08.2028
Complejos de Naftiridinafeno en Electrocatálisis Molecular Cooperativa
Project PID2024-161214NB-I00 funded by:
Project: PID2024-161214NB-I00
Entity: Ministerio de Ciencia, Innovación y Universidades
Validity: 01.09.2025-31.08.2028
Conjugacion Extendida Molecular En CO2RR Electroquimico
Project CNS2022-135765 funded by:
Project: CNS2022-135765
Entity: Ministerio de Ciencia, Innovación y Universidades
Validity: 01.09.2023-31.12.2025
Cooperative Molecular Electrocatalysis for eFuel Production
Project PID2021-126887NA-I00 funded by:
Project: PID2021-126887NA-I00
Entity: Junta de Andalucía
Validity: 01.09.2022-31.08.2025
Electrofuel Production by Cooperative Means
Project ProyExcel_00746 funded by:
Project: ProyExcel_00746
Entity: Junta de Andalucía
Validity: 02.12.2022-31.12.2025
Convocatoria Ramón y Cajal
Project RYC-2020- 2021/00001612 funded by:
Project: RYC-2020- 2021/00001612
Entity: Ministerio de Ciencia, Innovación y Universidades
Validity: 01.03.2022-30.09.2025
Molecular Means for Renewable Energy Storage and Fuel Production
Project ANR-18-MPGA-0012 funded by:
Project: ANR-18-MPGA-0012
Entity: Agence Nationale de la Recherche (ANR)
Validity: 01.01.2019-31.12.2023