Article
Chemistry, Physical
Juntao Liu, Jiayan Du, Feng Yu, Lan Gan, Guixia Liu, Zheng Huang
Summary: We designed and synthesized cobalt complexes of L2X-type ligands for olefin hydroboration while considering catalyst stability. The complex with iPr phosphinosubstituents showed broad scope, high functional group tolerance, and high catalytic activity in the hydroboration of terminal olefins with pinacolborane. It demonstrated selectivity for linear hydroboration reactions at elevated temperatures, including with olefins conjugated with arene or carbonyl groups that were difficult to achieve with previous catalysts.
Article
Chemistry, Multidisciplinary
Anthony Vivien, Laurent Veyre, Raphael Mirgalet, Clement Camp, Chloe Thieuleux
Summary: The catalytic hydrosilylation of alkenes is an important industrial reaction for obtaining functional organosilane compounds and cross-linked materials. Platinum-based catalysts are widely used, but efforts have been made to replace platinum with non-noble metals. A non-noble metal catalytic system using MnBr(CO)(5) has been developed and successfully employed in various olefin hydrosilylation reactions and the synthesis of cross-linked materials.
Article
Chemistry, Applied
Yu Liu, Jiayun Li, Ying Bai, Jiajian Peng
Summary: A series of nitrogen phosphine ligands were synthesized for investigating the hydrosilylation reaction of alkenes catalyzed using MCl2. Among them, the CoCl2/N,P-ligand catalyst system showed high catalytic activity and excellent selectivity, achieving close to 100% selectivity for beta-adduct.
APPLIED ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Applied
Haiquan Yang, Guoliang Chang, Xiaoyan Li, Hongjian Sun, Olaf Fuhr, Dieter Fenske
Summary: Two silyl [P,Si]-chelate cobalt hydrides were prepared and found to efficiently catalyze the hydrosilylation of olefins.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Maciej Skrodzki, Victor Ortega Garrido, Aurelio G. Csaky, Piotr Pawluc
Summary: This study reports a stable cobalt(II) complex that exhibits high catalytic activity and selectivity in hydrosilylation reactions, with unprecedented tolerance towards tertiary silanes. The catalytic system shows high regioselectivity for a variety of alkynes, resulting in the formation of alpha-vinylsilanes.
JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Anthony Ropp, Sophie Carenco
Summary: Phosphine-covered NiCo nanoparticles with a 1:1 metal ratio were found to activate Si-H bonds at room temperature, but it was unclear which metal was the active site. By designing nanoparticles with a nickel core and limited cobalt surface sites, researchers discovered that cobalt is the active site and its immediate neighbours of cobalt atoms enhance the reaction efficiency. Two phosphine ligands, PPh3 and PnBu(3), were used and PPh3 showed higher conversion rate compared to PnBu(3).
Article
Chemistry, Organic
Maciej Skrodzki, Violetta Patroniak, Piotr Pawluc
Summary: A bench-stable cobalt(II) complex, with a 3N-donor socket-type benzimidazole-imine-2H-imidazole ligand, is reported as an efficient precatalyst for regioselective hydrosilylation of terminal alkynes, providing high yields with excellent selectivity. This catalyst loading range of 0.5-0.05 mol % is among the most efficient reported for cobalt-catalyzed alkyne hydrosilylation in the literature.
Article
Chemistry, Inorganic & Nuclear
Katsuaki Kobayashi, Hiroshi Nakazawa
Summary: The search for an activator for the catalyst precursor [Co(tpy)Br-2] in the hydrosilylation of olefins with hydrosilane led to the discovery of K2CO3 as an effective activator. The ability of various salts to activate the catalyst was examined and compared, and it was determined that an excellent activator requires low MX lattice energy, high X-nucleophilicity, and a strong Si-X bond.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Xuchao Wang, Jing Xue, Zi-Qiang Rong
Summary: This study reports a highly efficient catalyst-tuned regio- and enantioselective hydroalkylation reaction for the divergent synthesis of chiral C2- and C3-alkylated pyrrolidines. The reaction uses readily available catalysts and chiral ligands to synthesize enantioenriched compounds with excellent regio- and enantioselectivity. It also demonstrates compatibility with complex substrates derived from a series of drugs and bioactive molecules, providing a distinct entry to more functionalized chiral N-heterocycles.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Hanna Stachowiak-Dluzynska, Krzysztof Kucinski, Bozena Wyrzykiewicz, Rhett Kempe, Grzegorz Hreczycho
Summary: Vinylsilanes are versatile chemical derivatives that are increasingly being used in various synthetic transformations. In this study, a novel cobalt-catalyzed procedure was developed for the selective hydrosilylation of internal aryl-, alkyl-, and silylalkynes. The use of cobalt complexes with triazine-based PNP pincer-type ligands enabled the exclusive syn-addition of primary and secondary silanes to C=C bonds, resulting in the efficient formation of (E)-silylalkenes and vicinal disilylalkenes with excellent stereoselectivity and regioselectivity. Unlike other transition metal-catalyzed procedures, no external additives were required as hydrosilanes served as both substrates and activators.
Article
Chemistry, Applied
Zehao Yu, Zijie Song, Chunshan Lu, Ying Bai, Jiayun Li, Jun Liu, Peng Liu, Jiajian Peng
Summary: Hydrosilylation reactions using metal-organic frameworks as catalysts hold great promise due to their high reactivity and sustainability. We have developed an efficient method using an air-stable MOF-cobalt catalyst for the hydrosilylation of olefins, with excellent reactivity, recyclability, and tolerance towards functional groups.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Magali Puillet, James Delorme, Delphine Crozet, Matthieu Humbert, David Gajan, Magali Bousquie, Delphine Blanc, Jean Raynaud, Vincent Monteil
Summary: Commercially available Ni(ii) and Co(ii) complexes act as catalysts for alkene/vinylsilane dehydrogenative silylation and hydrosilylation without external reducing agents. Ni is selective for DS products, while Co yields both HS and DS products, and all complexes efficiently induce silicone-oil crosslinking under a non-inert atmosphere.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Inorganic & Nuclear
David Decker, Zhihong Wei, Jabor Rabeah, Hans-Joachim Drexler, Angelika Brueckner, Haijun Jiao, Torsten Beweries
Summary: In this study, a Co(ii) PNNH pincer catalyst system was applied for the highly E-selective transfer semihydrogenation of internal diaryl alkynes. The catalyst system showed high activity, short reaction times, and operated under mild conditions.
INORGANIC CHEMISTRY FRONTIERS
(2022)
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)
Article
Chemistry, Inorganic & Nuclear
Carmen Antuna-Horlein, Fule Wu, Christophe Deraedt, Corinne Bouillet, Jean-Pierre Djukic
Summary: The reactivity of a 2-phenylpyridine-derived metallacycle towards Et3SiH and hydrides was studied. Treatment of the same Co(III) complex with Na[BHEt3] resulted in its decomposition into cobalt nanoparticles. The decomposition of the metallacycle involves the formation of a hydrido-cobalt(III) intermediate, which was detected by H-1 NMR spectroscopy. The Co nanoparticles produced from the metallacycle and Na[BHEt3] serve as catalysts for the hydrosilylation of arylketones into silylalkyl ethers.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Leon Escomel, Naime Soule, Emmanuel Robin, Iker Del Rosal, Laurent Maron, Erwann Jeanneau, Chloe Thieuleux, Clement Camp
Summary: We report a novel alkane elimination approach that involves the protonolysis of triisobutylaluminum by the acidic hydrides from Cp*IrH4. This strategy allows the synthesis of well-defined iridium aluminum polyhydride clusters with original structures and reactivities.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Thomas Galeandro-Diamant, Vincent Dardun, Moulay Tahar Sougrati, Lorenzo Stievano, Kirill A. Lomachenko, Laurent Veyre, Valerie Meille, Chloe Thieuleux
Summary: Non-crystalline and non-metallic iron-based nanoparticles were synthesized in solution from easily accessible commercial products in mild conditions. These nanoparticles were used to generate well-defined solids containing metallic iron or iron oxide nanoparticles. The non-crystallinity and organometallic character of the starting iron nanoparticles were found to be beneficial in generating a specific catalytic activity.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Laura Reyes, Lea Vilcocq, Marie-Line Zanota, Valerie Meille, Clemence Nikitine, Pascal Fongarland
Summary: The application of open cell foams as catalytic supports has gained development in recent years due to their large specific surface area, high void fractions, and enhanced internal mass transport. In this study, aluminum foams with different macropore sizes were used as supports for a TiO2-WOx catalyst and a structured packing material for reactors. The foams' geometric and structural features were characterized, and the optimized conditions achieved a maximum catalyst loading of 234 kg(catalyst) m(support)(-3) with maintained void fraction (>0.8). The structured catalyst demonstrated its performance and activity in a batch reactor for 3 catalytic runs, lasting for 18 hours.
Article
Chemistry, Inorganic & Nuclear
Vincent Dardun, Tania Pinto, Loic Benaillon, Laurent Veyre, Jules Galipaud, Clement Camp, Valerie Meille, Chloe Thieuleux
Summary: A simple protocol was used to synthesize small (<2 nm) crystalline Pd2Sn nanoparticles via the organometallic approach. These nanoparticles showed better catalytic performance in the Suzuki-Miyaura cross-coupling reaction compared to Pd nanoparticles, indicating a beneficial effect of tin on palladium catalysis.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Christopher Z. Ye, Iker Del Rosal, Michael A. Boreen, Erik T. Ouellette, Dominic R. Russo, Laurent Maron, John Arnold, Clement Camp
Summary: Reaction of potassium pentamethylcyclopentadienyl iridate tris-hydride with UCl4 and ThCl4 led to the generation of multimetallic complexes with different hydride bonding modes. Computational studies suggest that the bonding between U/Th and Ir is significant and involving f-orbitals. The variation in hydride bonding is attributed to differences in dispersion effects.
Article
Materials Science, Coatings & Films
Petros Abi Younes, Ashok-Kumar Yadav, Medet Zhukush, Van-Hoan Le, Herve Roussel, Marie-Ingrid Richard, Clement Camp, Kai Szeto, Gianluca Ciatto, Nathanaelle Schneider, Elsje Alessandra Quadrelli, Hubert Renevier, Nicolas Gauthier
Summary: Amorphous organic-inorganic hybrid thin films (Ti-thiolate) on thermal SiO2 substrate are converted into textured titanium disulfide (TiS2) ultrathin films through annealing under Ar/H-2 atmosphere. Two annealing strategies were investigated to control the mineralization process. The stoichiometry and crystallinity of the films were characterized by various techniques.
JOURNAL OF VACUUM SCIENCE & TECHNOLOGY A
(2023)
Article
Biochemistry & Molecular Biology
Xiaolong Ji, Essyllt Louarn, Fabienne Fache, Laurent Vanoye, Anne Bonhomme, Isabelle Pitault, Valerie Meille
Summary: The dibenzyltoluene (H0-DBT) heat transfer oil, which is used as a liquid organic hydrogen carrier, contains various isomers of dibenzyltoluene and (benzyl)benzyltoluene. To understand its composition and hydrogenation mechanism, GC-MS analysis was conducted to identify all compounds in the oil. Synthesized DBTs were used to confirm peak attribution, and NMR and Raman spectroscopies were employed to characterize pure compounds. Additionally, a fast-GC analysis method was developed to quickly determine the degree of hydrogenation of the mixture.
Article
Chemistry, Physical
Ekaterina Bellan, Farahnaz Maleki, Martin Jakoobi, Pierre Fau, Katia Fajerwerg, Delphine Lagarde, Andrea Balocchi, Pierre Lecante, Julien Trebosc, Yijue Xu, Zhehong Gan, Lauriane Pautrot-d'Alencon, Thierry Le Mercier, Hiroki Nagashima, Gianfranco Pacchioni, Olivier Lafon, Yannick Coppel, Myrtil L. Kahn
Summary: In this study, sulfur vacancies in ZnS nanoplatelets were characterized by high-field and DNP-enhanced solid-state NMR of S-33 and Zn-67 nuclei, as well as DFT modeling. The research showed that a significant number of Zn and S atoms are located near the surface covered by dodecylamine and the deviation from stoichiometry is due to sulfur vacancies.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Amira Jabbari-Hichri, Amine Bourouina, Pierre-Francois Biard, Audrey Denicourt-Nowicki, Alain Roucoux, Marie-Line Zanota, Fabrice Campoli, Claude de Bellefon, Valerie Meille
Summary: In this study, open cell foam materials were used as supports for Pd/C, Siliacat-Pd(0), Pd(ii)-DPP catalyst powders, and Pd(0) NPs, allowing leaching of active species for the Suzuki-Miyaura C-C coupling reaction. It was found that trace amounts of Pd in the range 30-300 ppb were sufficient for the reaction, while maintaining a low pressure drop.
REACTION CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Inorganic & Nuclear
Sebastien Lassalle, Julien Petit, Rosalyn L. Falconer, Valentin Herault, Erwann Jeanneau, Chloe Thieuleux, Clement Camp
Summary: This article describes the reaction of Cp*IrH4 with Hf(Np)(4) to form a heterobimetallic complex. The reactions of this complex with NpLi or benzyl potassium were investigated, resulting in the formation of different complexes.
Article
Chemistry, Multidisciplinary
Leon Escomel, Daniel F. Abbott, Victor Mougel, Laurent Veyre, Chloe Thieuleux, Clement Camp
Summary: Iridium-aluminium nanoparticles grafted onto silica show enhanced catalytic performances in methane H/D exchange, compared to monometallic iridium nanoparticles. The catalyst exhibits high TON values and remains active after exposure to air, indicating good robustness.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Anthony Vivien, Laurent Veyre, Raphael Mirgalet, Clement Camp, Chloe Thieuleux
Summary: The low temperature regioselective hydrosilylation of various alkenes with Mn-2(CO)(10) under UV irradiation is achieved with Mn loadings as low as 1 mol%, in the absence of additives and with excellent selectivity and yields. The generation of a manganese radical allows the anti-Markovnikov hydrosilylation products to be selectively obtained in yields up to 99%.
CHEMICAL COMMUNICATIONS
(2022)
