Correction
Chemistry, Inorganic & Nuclear
Alejandra Gomez-Espana, Jorge L. Lopez-Morales, Belinda Espanol-Sanchez, Pilar Garcia-Orduna, Fernando J. Lahoz, Manuel Iglesias, Francisco J. Fernandez-Alvarez
Summary: This article investigates the catalytic performance of iridium complexes in the dehydrogenation of formic acid and examines the effect of auxiliary ligands on the catalytic performance.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Organic
Xin Liu, Wen-Zhe Dong, Yang Li, Xiaoqiang Yu, Wan-Hui Wang, Yuichiro Himeda, Ming Bao
Summary: In this study, an efficient and selective strategy for the synthesis of α-substituted ketones via borrowing hydrogen was reported. β-Alkylation of secondary alcohols to α-substituted ketones was catalyzed by an amidato Ir(III) complex in water. The method showed high yields and good tolerance to various substrates.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Physical
Nicolas Lentz, Martin Albrecht
Summary: This article reports on a highly efficient iridium-based catalyst for formic acid dehydrogenation. The catalyst exhibits high turnover frequencies and turnover numbers, and is characterized by its low cost and easy accessibility, making it suitable for industrial applications.
Article
Chemistry, Inorganic & Nuclear
Nicolas Lentz, Alicia Aloisi, Pierre Thuery, Emmanuel Nicolas, Thibault Cantat
Summary: Two new cobalt complexes with a phosphoramine-containing pincer ligand exhibited excellent catalytic activity in the dehydrogenation of formic acid without the need for bases or additives. Mechanistic study showed the presence of ligand-metal cooperativity with intermolecular hydrogen bonding, influenced by the concentration of formic acid.
Article
Chemistry, Physical
Maria Gutierrez-Blanco, Carolin A. M. Stein, Carmina Alfonso, Eva Guillamon, Vicent S. Safont, Ivan Sorribes, Henrik Junge, Matthias Beller, Rosa Llusar
Summary: In this study, a protocol for formic acid dehydrogenation assisted by biomimetic Mo3S4 clusters has been developed, boosting the activity of Mo3S4 catalysts. Experiments and theoretical calculations have confirmed that formate substitution products are the catalytically active species.
Review
Chemistry, Physical
Manuel Iglesias, Francisco J. Fernandez-Alvarez
Summary: Formic acid is a potential liquid organic hydrogen carrier with high volumetric concentration of H-2, which allows for safe storage and transportation of hydrogen. Research on selective catalytic dehydrogenation of formic acid using precious metal catalysts has gained attention. Development of catalytic systems based on non-precious metals is also of interest.
Article
Nanoscience & Nanotechnology
Yue Liu, Fangyu Fu, Lionel Salmon, Bruno Espuche, Sergio Moya, Murielle Berlande, Jean-Luc Pozzo, Jean-Rene Hamon, Didier Astruc
Summary: A new type of catalyst support, involving the addition of metal ion precursors to core-shell ZIF-8@ZIF-67, was proposed and its performance exceeded that of nanocatalysts in ZIF-8 or ZIF-67. Under visible-light illumination, the optimized nanocatalysts achieved a turnover frequency of 430 h-1 for selective formic acid dehydrogenation. The superiority of ZIF-8@Pd2Ag1@ZIF-67 over other catalysts was confirmed in the benchmarking model of 4nitrophenol reduction, indicating the interest in this novel catalyst design.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Physical
Vinay Arora, Eileen Yasmin, Niharika Tanwar, Venkatesha R. Hathwar, Tushar Wagh, Sunil Dhole, Akshai Kumar
Summary: A series of pincer-ruthenium complexes based on bis(imino)pyridine ligands were synthesized and characterized. These complexes showed high efficiency in the reforming of methanol in water, with (Cy2NNN)-RuCl2(PPh3) being the most efficient catalyst. By using KOtBu as the base, the reforming reaction achieved good results at low temperatures. The involvement of C-H activation in the catalytic cycle and the rate-determining step was confirmed through isotope-labeling studies and DFT calculations. The current catalytic system offers promise in the transformation of methanol to hydrogen and formic acid with high selectivity.
Article
Materials Science, Multidisciplinary
Hanen Abdelli, Houeida Issa Hamoud, Juan Pablo Bolletta, Arnold Paecklar, Afrah Bardaoui, Krassimir L. Kostov, Ewelina Szaniawska, Antoine Maignan, Christine Martin, Mohamad El-Roz
Summary: A highly efficient CuFe2O4-based photocatalyst is reported for the photo-catalytic dehydrogenation of formic acid under visible light at room temperature. The catalyst exhibits high selectivity and stability, making it a promising material for photocatalytic dehydrogenation. This study provides a new route to design cost-effective Cu-based photocatalysts for visible-light driven reactions.
APPLIED MATERIALS TODAY
(2023)
Article
Chemistry, Organic
Wenlong Ren, Jinzi Huang, Yian Shi
Summary: An effective Pd-catalyzed regioselective hydroformylation process using N-formylsaccharin or 2,4,6-trichlorophenyl formate along with formic acid is described. Linear aldehydes can be obtained in high yield and with a high linear/branched ratio. The reaction is operationally simple without the need for external CO and H2.
Article
Chemistry, Physical
Wenrui Yan, Jin Zhang, Shanfu Lu, San Ping Jiang, Yan Xiang
Summary: In high-temperature formic acid fuel cells, the dehydrogenation behavior of formic acid is crucial for boosting cell output performance. The concentration of formic acid affects the amount of hydrogen produced, while reducing water vapor content may promote dehydration and inhibit dehydrogenation. Dehydration leads to the release of carbon monoxide, but it does not significantly affect the power output of the fuel cell.
JOURNAL OF POWER SOURCES
(2022)
Article
Chemistry, Physical
Jialing Xu, Yawen Li, Xiaofen Chen, Guifang Li, Jiaqi Huo, Lishan Jia
Summary: Researchers have successfully constructed Ni@0.20RGO nanomaterial with excellent catalytic performance for dehydrogenation of formic acid to hydrogen at near room temperature. This catalytic performance is comparable to some of the most active non-noble metal catalysts, providing new possibilities for promoting the development of clean energy technologies.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2022)
Article
Chemistry, Physical
Tong Liu, Zongji Zhang, Ling Yan, Zhibin Zhang, Yi Zhang, Yansheng Yin
Summary: A simple wet chemical method was used to prepare two-dimensional transition metal carbides (MXene), and Pd metal nanoparticles were loaded on its surface to catalyze the dehydrogenation of formic acid. The prepared Pd/PDA-MXene catalyst exhibited excellent catalytic activity in formic acid decomposition process, and maintained stable activity in five consecutive catalytic cycles.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2021)
Article
Chemistry, Physical
Julia B. Curley, Nicholas E. Smith, Wesley H. Bernskoetter, Mehmed Z. Ertem, Nilay Hazari, Brandon Q. Mercado, Tanya M. Townsend, Xiaoping Wang
Summary: The iron pincer complex ((PNP)-P-iPr)Fe(H)(CO) is an active catalyst, but rapid decomposition limits its performance. Analysis suggests that catalytic intermediates may decompose via a bimolecular pathway, leading to the formation of dimeric species. The study provides strategies for improving catalysis and enhancing the performance of the catalyst in formic acid dehydrogenation.
Review
Chemistry, Multidisciplinary
S. Hafeez, E. Harkou, A. Spanou, S. M. Al-Salem, A. Villa, N. Dimitratos, G. Manos, A. Constantinou
Summary: This paper reviews the recent progress in hydrogen production from various technologies and presents the advantages of formic acid as a hydrogen supply source and the catalysts and reactors for formic acid reaction.
MATERIALS TODAY CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Miguel Gonzalez-Lainez, M. Victoria Jimenez, Ramon Azpiroz, Vincenzo Passarelli, F. Javier Modrego, Jesus J. Perez-Torrente
Summary: This study evaluates a set of neutral and cationic Ir(I) compounds as catalyst precursors for the N-methylation of aniline using methanol. The results show that the compounds with NHC and -OMe ligands can selectively transform aromatic and heterocyclic amines into N-methylamino derivatives with high selectivity under low catalyst loading and substoichiometric amounts of base. Mechanistic investigations suggest the involvement of Ir(I) intermediates and the methoxo complex as the catalytic active species.
Article
Materials Science, Multidisciplinary
Ramon Azpiroz, Marina Borraz, Aida Gonzalez, Catalina Mansilla, Manuel Iglesias, Jesus J. Perez-Torrente
Summary: A porous TiO2 coating with good photocatalytic activity was prepared on glass using the ALD/MLD method.
Article
Chemistry, Inorganic & Nuclear
Miguel Gonzalez-Lainez, Miguel Gallegos, Julen Munarriz, Ramon Azpiroz, Vincenzo Passarelli, M. Victoria Jimenez, Jesus J. Perez-Torrente
Summary: Copper(I) compounds supported by flexible functionalized NHC-based polydentate ligands exhibit high catalytic activity in Cu-catalyzed azide-alkyne cycloaddition reactions. The polymeric compounds break down into more compact tetranuclear compounds with the same coordination mode as the NHC ligands. These compounds efficiently catalyze the click reaction under inert conditions at room temperature with very low catalyst loading, providing 1,4-disubstituted 1,2,3-triazole derivatives.
Article
Biochemistry & Molecular Biology
Ramon Azpiroz, Mert Olgun Karatas, Vincenzo Passarelli, Ismail Ozdemir, Jesus J. Perez-Torrente, Ricardo Castarlenas
Summary: A series of mixed bis-NHC rhodium(I) complexes have been synthesized using two different NHC ligands and eta(2)-olefin. The steric hindrance of both NHC ligands and the eta(2)-olefin plays a critical role. Similarly, mixed coumarin-functionalized bis-NHC rhodium complexes have been prepared by reacting mono NHC complexes with the corresponding azolium salt in the presence of an external base. Both synthetic procedures have high selectivity and yield mixed bis-NHC rhodium complexes.
Article
Chemistry, Inorganic & Nuclear
Susana Garcia-Abellan, Vincenzo Passarelli, Manuel Iglesias
Summary: 2a and 2b [Ir(CI)(COD)(NHC)] (1,5-cyclooctadiene as COD) were synthesized by transmetallation from NHC-Ag complexes. Analogously, [Rh(CI)(COD)(NHC)] (4) was prepared. [Ir({kappa-C,N-(NHC-acetamide-1H)}(COD)] (3c) was synthesized by transmetallation from deprotonated NHC-Ag complex. [IrCp*({kappa-C,N-(NHC-acetamide-1H)}] (5) (Cp*=pentamethylcyclopentadienyl) was obtained analogously. [Ir(CI)(CO)(2)(NHC)] (6) and [Ir({kappa-C,N-(NHC-acetamide-1H)}(CO)(2)] (7) were prepared by carbonylation of 2b and 3c, respectively. The catalytic activity of these complexes in formic acid dehydrogenation was evaluated under solventless conditions, in the presence of water as a cosolvent, and in a 5 : 2 HCOOH/Et3N mixture, with the best TOF values obtained in the latter case. Stoichiometric experiments suggest COD hydrogenation as the preactivation step.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Polymer Science
Pablo Hermosilla, Daniel Funes-Hernando, Ricardo Castarlenas, Andrea Di Giuseppe, Ramon Azpiroz, Eugenio Vispe, Jesus J. Perez-Torrente
Summary: The catalytic system of [Rh(mu-Cl)(IPr)(eta 2-coe)]2/pyridine efficiently facilitates the polyhydrothiolation reaction between dithiols and dialkynes, resulting in the formation of sulfur-rich poly(vinylidene sulfide)s with high molecular weights and high vinylidene sulfide content. The combination of different types of dithiols and dialkynes allows the preparation of poly(vinylidene sulfide)s with varying properties.
EUROPEAN POLYMER JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Ana Luque-Gomez, Pilar Garcia-Orduna, Fernando J. Lahoz, Manuel Iglesias
Summary: A new method for preparing Co(I)-NHC complexes has been developed, which involves the direct reaction of imidazolium salts with Co(0) complex. The obtained complexes have shown efficient catalytic activity in the reductive amination of furfural and levulinic acid, using silanes as reducing agents. The side reaction of hydrosilylation process, dehydrocoupling of the silane, has also been observed.
DALTON TRANSACTIONS
(2023)
Correction
Chemistry, Inorganic & Nuclear
Alejandra Gomez-Espana, Jorge L. Lopez-Morales, Belinda Espanol-Sanchez, Pilar Garcia-Orduna, Fernando J. Lahoz, Manuel Iglesias, Francisco J. Fernandez-Alvarez
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Miguel Gonzalez-Lainez, M. Victoria Jimenez, Vincenzo Passarelli, Jesus J. Perez-Torrente
Summary: Neutral and cationic cyclooctadiene rhodium(i) complexes with a lutidine-derived polydentate ligand have been synthesized and found to efficiently catalyze the hydrosilylation of 1-hexyne with high selectivity. These catalysts exhibit a different β-(Z) selectivity compared to previously reported rhodium(i) catalysts based on 2-picolyl-functionalized NHC ligands. Kinetic studies suggest an energy barrier of 19.8±2.0 kcal mol(-1) for the hydrosilylation reaction.
DALTON TRANSACTIONS
(2023)
Article
Urology & Nephrology
Susana Garcia-Abellan, Vincenzo Passarelli, Manuel Iglesias
Summary: Two Ir complexes, 2a and 2b, with the ligand [Ir(CI)(COD)(NHC)] (COD=1,5-cyclooctadiene), were synthesized through transmetallation from NHC-Ag complexes. Analogously, another Rh complex, 4, was prepared using the same method. By transmetallation from the deprotonated NHC-Ag complex, another Ir complex, 3c, with the ligand [Ir({kappa-C,N-(NHC-acetamide-1H)}(COD)], was synthesized. Similarly, [Ir(CI)(CO)(2)(NHC)] (6) and [Ir({kappa-C,N-(NHC-acetamide-1H)}(CO)(2)] (7) were obtained through carbonylation of 2b and 3c respectively. The catalytic activity of these complexes in formic acid dehydrogenation was evaluated, with the highest turnover frequency (TOF) observed in the presence of a 5:2 HCOOH/Et3N mixture. Stoichiometric experiments suggested COD hydrogenation as the preactivation step.
Article
Chemistry, Inorganic & Nuclear
Alejandra Gomez-Espana, Jorge L. Lopez-Morales, Belinda Espanol-Sanchez, Pilar Garcia-Orduna, Fernando J. Lahoz, Manuel Iglesias, Francisco J. Fernandez-Alvarez
Summary: A comparative study of the catalytic activity of two iridium(III) complexes has been performed, and it was found that complex 3 showed the highest activity in the solventless formic acid dehydrogenation reaction at 373 K. The best performance was achieved at 353 K, with a reaction rate of approximately 1210 h(-1) and no observable CO.
DALTON TRANSACTIONS
(2023)
Correction
Chemistry, Inorganic & Nuclear
Alejandra Gomez-Espana, Jorge L. Lopez-Morales, Belinda Espanol-Sanchez, Pilar Garcia-Orduna, Fernando J. Lahoz, Manuel Iglesias, Francisco J. Fernandez-Alvarez
Summary: This article investigates the catalytic performance of iridium complexes in the dehydrogenation of formic acid and examines the effect of auxiliary ligands on the catalytic performance.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Susana Garcia-Abellan, Daniel Barrena-Espes, Julen Munarriz, Vincenzo Passarelli, Manuel Iglesias
Summary: The novel P-N ligand based on a benzotriazole scaffold was prepared and used to synthesize chelate complexes. These complexes acted as catalysts in the fluorination reactions of aromatic and aliphatic acyl chlorides. The reaction rate and substrate scope were improved by using organic carbonates as solvents. Comparative studies and theoretical calculations were conducted to understand the reaction mechanism.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Marco Palmese, Jesus J. Perez-Torrente, Vincenzo Passarelli
Summary: This study investigates the reaction mechanism and structures of the iridium(III) derivatives produced from the reactions of [IrCl(cod)(SiNP)] and [Ir{kappa C-3,P,P '-(SiNP-H)}(cod)] with various oxidants. The reactions include allyl chloride and tert-butyl isocyanide, as well as [FeCp2]X, I-2, and CF3SO3CH3. The crystal structures of selected compounds confirm the products of these reactions.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Marco Palmese, Jesus J. Perez-Torrente, Vincenzo Passarelli
Summary: In this study, the iridium(I)-aminophosphane complex [Ir{kappa C-3,P,P'-(SiNP-H)}(cod)] was prepared by reaction of [IrCl(cod)(SiNP)] with KCH3COO. It was found that this reaction proceeds through an unexpected outer sphere mechanism. Various iridium(III) derivatives were obtained by reacting [IrCl(cod)(SiNP)] or [Ir{kappa C-3,P,P'-(SiNP-H)}(cod)] with different oxidants. The crystal structures of selected compounds were determined.
DALTON TRANSACTIONS
(2023)