Article
Chemistry, Physical
William G. Whitehurst, Junho Kim, Stefan G. Koenig, Paul J. Chirik
Summary: The cationic bis(phosphine) cobalt(I) arene complex was studied as a precatalyst for the three-component coupling reaction. However, hydrovinylation from the alkene and alkyne was favored over three-component coupling, indicating the role of C-H activation. Deuterium labeling supported the mechanism involving β-H elimination from a putative cobalt(III)-alkyl,aryl intermediate formed after C-H activation. The selectivity of C(sp(3))-C(sp(2)) reductive elimination versus β-H elimination from the cobalt(III)-alkyl,aryl intermediate was determined by varying the arene and alkene coupling partners.
Article
Chemistry, Multidisciplinary
Yue Pang, Markus Leutzsch, Nils Noethling, Felix Katzenburg, Josep Cornella
Summary: The study reports a hydrodefluorination reaction of polyfluoroarenes catalyzed by bismuthinidenes, involving a Bi(I)/Bi(III) redox cycle with C(sp(2))-F oxidative addition, F/H ligand metathesis, and C(sp(2))-H reductive elimination steps. Spectroscopic evidence supports the formation of a transient Phebox-Bi(III)(4-tetrafluoropyridyl) hydride during catalysis, which decomposes at low temperature to regenerate the propagating Phebox-Bi(I). This protocol highlights a unique catalytic example of a main-group center performing three elementary organometallic steps in a low-valent redox manifold.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Oliver P. E. Townrow, Simon B. Duckett, Andrew S. Weller, Jose M. Goicoechea
Summary: The ligand exchange reactions lead to clusters with coordinatively unsaturated rhodium(i) centers, which can act as catalysts for H/D exchange and alkene isomerisation. Protonation of these clusters results in cationic rhodium-hydride complexes, showing their activity in both H-H and C-H bond activation processes.
Article
Chemistry, Multidisciplinary
Jia Jiang, Bei Cao, Yuting Chen, Hejiang Luo, Jiaying Xue, Xiaolin Xiong, Taotao Zou
Summary: The stable alkylgold(III) complexes can undergo unprecedented photo-induced beta-hydride elimination within tumors, releasing bioactive [Au-III-S] adducts that exhibit efficient tumor-selective uptake and antitumor activities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Gyeongjin Park, Mohammadjavad Karimi, Wei-Chun Liu, Francois P. Gabbai
Summary: By discovering suitable metal platforms and utilizing specific ligands, efficient photoreductive halogen elimination reactions can be achieved under visible light. The xanthylium unit in the [7](+) complex plays a crucial role in promoting the high quantum yield of the visible-light-induced photoreduction process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Andie R. Delaney, Asja A. Kroeger, Michelle L. Coote, Annie L. Colebatch
Summary: This study investigates the bimetallic beta-hydride elimination reaction in nickel complexes, providing further understanding of bimetallic elementary reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Alexandre Genoux, Michal Biedrzycki, Estibaliz Merino, Eva Rivera-Chao, Anthony Linden, Cristina Nevado
Summary: A new family of cationic, bidentate gold(III) fluoride complexes have been prepared and characterized, showing reactivity with cyano and acetylene nucleophiles. The resulting arylgold(III)C(sp) complexes exhibit higher rates of C(sp(2))-C(sp) bond formation compared to phosphine-based monodentate systems.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Alexander Q. Kane, Alec M. Esper, Keith Searles, Christian Ehm, Adam S. Veige
Summary: The study advances the understanding of C-C bond cleavage through DFT characterization on a substrate and catalyst, with a focus on selectivity in C-C bond cleavage events. The selectivity rules established will guide future experimental work and catalyst design.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Inorganic & Nuclear
Ba L. Tran, Jeremy D. Erickson, Amy L. Speelman, R. Morris Bullock
Summary: The ability of Cu-H complexes to selectively insert unsaturated hydrocarbons has made them valuable catalysts. The formation of Cu allyl intermediates from 1,3-dienes and Cu hydrides is a promising strategy. However, there is limited research on the mechanistic studies and characterization of intermediates in Cu-H catalysis. This study explores the steric effects of NHC ligands on two key elementary steps of CuH-catalyzed carbonyl allylation and provides insights for a range of catalytic reactions.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Sara Fernandez-Moyano, Guillermo Marcos-Ayuso, Marconi N. Penas-Defrutos, Camino Bartolome, Pablo Espinet
Summary: F-19 NMR monitoring reveals that heating trans-[Au(III)Rf(2)I(2)](-) solutions (Rf = C6F3Cl2-3,5) leads to the formation of cis-[AuRf(2)I(2)](-), [AuRf(3)I](-), and [AuRfI(3)](-) via kinetic competition between isomerization and Rf/I scrambling. The easy reductive elimination of Rf-I from [AuRfI(3)](-) (also forming [AuI2](-)) drives the system evolution, providing faster kinetics than any Rf-Rf couplings from the coexisting species, which hinders the desired thermodynamically preferred C-C coupling. A kinetic model is proposed, where I- dissociation triggers both isomerization and transmetalation steps, which is consistent with the experimental data. DFT calculations support that the lower bond strength of Au-III-I compared to other halides leads to a pathway switch, making C-I coupling kinetically preferred. Therefore, it is advisable to avoid C-I coupling in reactions seeking C-C coupling.
CHEMICAL COMMUNICATIONS
(2023)
Article
Engineering, Chemical
Shiyu Pan, Zhihui Zhai, Kai Yang, Yao Xiang, Shoufeng Tang, Yating Zhang, Tifeng Jiao, Qingrui Zhang, Deling Yuan
Summary: In this study, Fe(III) was loaded on beta-Lactoglobulin amyloid fibrils for efficiently activating peroxydisulfate (PDS) to remove organics in water. The synthesized material exhibited excellent stability and applicability for degradation of organic pollutants.
SEPARATION AND PURIFICATION TECHNOLOGY
(2022)
Article
Chemistry, Physical
Qiyuan He, Ken Yamazaki, Yusuke Ano, Naoto Chatani
Summary: This study reports the palladium-catalyzed reaction of 2-methylbenzamides with acrylic esters, resulting in the production of isoquinolinones. The reaction selectively occurs at the ortho methyl C-H bond via a six-membered palladacycle, rather than at the ortho C-H bond via a five-membered palladacycle. The key to the success of the reaction is the use of maleic anhydride as a ligand. Computational analyses indicate that the coordination of the maleic anhydride ligand greatly stabilizes the transition state for beta-hydride elimination and accelerates the reaction rate.
Article
Chemistry, Multidisciplinary
Christof Matt, Andreas Orthaber, Jan Streuff
Summary: A catalytic enantioselective beta-O-elimination reaction is reported, which involves a zirconium-catalyzed asymmetric opening reaction to achieve chiral beta-O-elimination. The reaction proceeds under mild conditions, with low catalyst loadings, and produces chiral monoprotected cis-1,2-diols in good yield and enantiomeric excess. Combination with other reactions also allows access to additional diol and aminoalcohol building blocks.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Artur P. Durajski, Radoslaw Szczesniak
Summary: The study found that carbonaceous lanthanum hydride LaC2H8 can exhibit superconductivity under high pressure, with a relatively high superconducting critical temperature.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Sneha Mullassery, K. Yuvaraj, Deepak Dange, Dafydd D. L. Jones, Iker del Rosal, Ross O. Piltz, Alison J. Edwards, Laurent Maron, Cameron Jones
Summary: A reduction reaction between amido- and aryloxy-aluminum dihydride complexes and β-diketiminato dimagnesium(I) reagents resulted in the formation of deep red mixed valence aluminum hydride cluster compounds. The clusters have an average Al oxidation state of +0.66, the lowest observed for any well-defined aluminum hydride compound. The clusters exhibit distorted octahedral Al-6 cores with zero-valent Al axial sites and mono-valent AlH2- equatorial units.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Taline Kerackian, Antonio Reina, Tetiana Krachko, Hugo Boddaert, Didier Bouyssi, Nuno Monteiro, Abderrahmane Amgoune
Summary: The novel Ni/photoredox-catalyzed acylation method utilizes C-N bond activation of amides and a radical relay mechanism involving hydrogen-atom transfer, offering an operationally simple approach to accessing alkyl ketones under very mild conditions. The use of bench-stable N-acyl imides as acyl-transfer reagents further simplifies the protocol.
Article
Agriculture, Multidisciplinary
Laura Estevez, Marta Queizan, Ricardo A. Mosquera, Lucia Guidi, Ermes Lo Piccolo, Marco Landi
Summary: The study found evidence for the formation of anthocyanin-metalloid complexes through a combination of experimental and computational data, with germanium showing a higher ability to bind to anthocyanins than boron. Among the envisioned complexes, those labeled as b1, b2, and b3 exhibit UV-vis spectra compatible with experiments.
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
(2021)
Article
Crystallography
Yassine Aimene, Romain Eychenne, Frederic Rodriguez, Sonia Mallet-Ladeira, Nathalie Saffon-Merceron, Jean-Yves Winum, Alessio Nocentini, Claudiu T. Supuran, Eric Benoist, Achour Seridi
Summary: In this work, two classes of Carbonic Anhydrase inhibitors, sulfonamide and coumarin derivatives, were synthesized and evaluated for their inhibitory activity against hCA isoforms. The compounds showed high selectivity and potential anti-cancer properties, with coumarin derivatives demonstrating strong inhibition against tumor-associated isoforms. Molecular docking calculations were performed to rationalize the results and investigate the inhibition profiles at the tumor-associated CA active site.
Article
Chemistry, Multidisciplinary
Omar Sadek, Arnaud Le Gac, Nereida Hidalgo, Sonia Mallet-Ladeira, Karinne Miqueu, Ghenwa Bouhadir, Didier Bourissou
Summary: A new method has been developed for the synthesis of phosphine-boranes, featuring simplicity, efficiency, and broad substrate scope. The key intermediates were identified as P-stabilized borenium cations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Oleksandr Ivanchenko, Maksym Odnoroh, Sonia Mallet-Ladeira, Marc Guerre, Stephane Mazieres, Mathias Destarac
Summary: A new symmetrical trithiocarbonate, Bis(2-cyanopropan-2-yl)trithiocarbonate, was synthesized with a highly effective route. This trithiocarbonate enabled the preparation of a high-molar-mass triblock copolymer with unprecedented control in RAFT polymerization, exhibiting typical thermoplastic elastomer behavior in rheology measurements.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Marc Camats, Isabelle Favier, Sonia Mallet-Ladeira, Daniel Pla, Montserrat Gomez
Summary: In this study, imidazo[1,5-a]pyridine heterocycles were successfully synthesized via Cu(II)-mediated functionalization of alpha '-C(sp(3))-H bonds of pyridinylaldimines and subsequent cyclization. The strategy utilized the directing ability of heteroleptic aldimine and pyridine groups in the substrate to selectively functionalize alpha '-methylene groups over distant methyl or methylene groups. The observed correlation between the nature of anionic ligands bonded to copper and the chemoselectivity of the C(sp(3))-H activation process suggests a concerted metalation-deprotonation pathway prior to cyclization.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Physical
Jessica Rodriguez, David Vesseur, Alexis Tabey, Sonia Mallet-Ladeira, Karinne Miqueu, Didier Bourissou
Summary: A (MeDalphos)AuCI complex has been discovered to efficiently catalyze the cross-coupling reaction of indoles and allyl acetates/alcohols. The reaction tolerates various functional groups and selectively produces branched C3-allylated products. It utilizes the hemilabile character of the P<^>N ligand.
Article
Chemistry, Multidisciplinary
Yael Juarez-Martinez, Pablo Labra-Vazquez, Alejandro Enriquez-Cabrera, Andres F. Leon-Rojas, Diego Martinez-Bourget, Pascal G. Lacroix, Marine Tasse, Sonia Mallet-Ladeira, Norberto Farfan, Rosa Santillan, Gabriel Ramos-Ortiz, Jean-Pierre Malval, Isabelle Malfant
Summary: This study presents four ruthenium nitrosyl (RuNO) complexes, which have well-characterized crystal structures and spectroscopic features. These complexes show high molecular cross-sections in two-photon absorption and are capable of releasing NO center dot under irradiation, making them promising for drug delivery based on two-photon absorption.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Fatima Zohra Chiboub Fellah, Carine Duhayon, Sonia Mallet-Ladeira, Laure Vendier, Jean-Pierre Costes
Summary: This study confirms the challenge of preparing main ligands that can coordinate 3d and 4f ions and introduce asymmetric centers near Ln ions. Despite difficulties in complexation with LnIII ions, an original reaction pathway was utilized to generate tetranuclear complexes with ferromagnetic Cu-Ln interactions.
Article
Chemistry, Physical
Taline Kerackian, Didier Bouyssi, Guillaume Pilet, Maurice Medebielle, Nuno Monteiro, Julien C. Vantourout, Abderrahmane Amgoune
Summary: This article describes the development and in-depth study of a cross-electrophile coupling of alkyl N-acyl imides with alkyl halides using nickel catalysis and electrochemistry. The method utilizes the stability and easy access of N-acyl imides to selectively synthesize dissymmetric dialkyl ketones. Mechanistic studies reveal the generation of alkyl radicals through single-electron oxidation of alkyl bromides by electrogenerated (bpy)Ni(I) species. The reaction of alkyl N-acyl imides with (bpy)Ni(0) and (bpy)Ni(I) species leads to Ni(II) acyl intermediates. A comprehensive mechanistic picture of this selective cross-electrophile coupling is achieved through these investigations.
Article
Crystallography
Isabelle Sasaki, Sonia Mallet-Ladeira
Summary: The crystal structures of two platinum complexes have been determined by X-ray diffraction. Both complexes crystallize in the monoclinic space group C2/c and have similar unit cell dimensions.
JOURNAL OF CHEMICAL CRYSTALLOGRAPHY
(2023)
Article
Chemistry, Multidisciplinary
Tingjun Hu, Mohammad Jaber, Gael Tran, Didier Bouyssi, Nuno Monteiro, Abderrahmane Amgoune
Summary: We have developed a nickel hydride-catalyzed methodology that can selectively convert internal alkynes to E- or Z-alkenes under mild conditions. The process involves a dual nickel/photoredox catalytic system and triethylamine, which acts as both a sacrificial reductant and a source of hydrogen atoms. Mechanistic studies reveal that the control of the stereoselectivity is determined by a final protonolysis step that can be tuned by adjusting the pKa of an alcohol additive.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Renhe Tang, Julien Petit, Yi Yang, Achim Link, Florian Bachle, Marie-Eve L. Perrin, Abderrahmane Amgoune, Anis Tlili
Summary: The nickel-catalyzed trifluoromethylselenolation of aryl and vinyl triflates has been studied in this research, including the development of synthesis methods and understanding the reaction mechanism. The Xantphos/Ni(COD)(2) catalytic system is found to be efficient in synthesizing aryl and vinyl trifluoromethylselenides, and the key steps of the catalytic cycle have been investigated through experimental and computational mechanistic studies. The results support a Ni-0/Ni-II process.
Article
Chemistry, Multidisciplinary
Rosa Carballo, Ana Belen Lago, Maria Vazquez-Toiran, Laura Estevez, Ezequiel M. Vazquez-Lopez
Summary: An investigation of the coordination chemistry of a Schiff-based ligand (HL) towards Ni(II) acetate was performed using single crystal X-ray diffraction. This study isolated two compounds [Ni(L)(2)]center dot H2O (2) and [Ni(HL)(2)(H2O)(2)](CH3CO2)(2)center dot 2CH(3)CH(2)OH (1a). Two solvated complexes [Ni(L)(2)]center dot solvent (2a, 2b) were also obtained as single crystals. The reactivity of compound 2 with 1,2-di(4-pyridyl)ethylene (bpe) yielded single crystals of [Ni(L)(2)(bpe)(2)]center dot solvent (3).
Article
Chemistry, Multidisciplinary
Gyorgy Szaloki, Julien Babinot, Vlad Martin-Diaconescu, Sonia Mallet-Ladeira, Yago Garcia-Rodeja, Karinne Miqueu, Didier Bourissou
Summary: Chelating P<^>P and hemilabile P<^>N ligands were found to oxidize Au(i) complexes by o-benzoquinones. The resulting Au(iii) catecholate complexes were characterized and the reversibility of the transformation was confirmed. DFT calculations provided insights into the structure and stability of the Au(i) o-quinone and Au(iii) catecholate forms.