Review
Chemistry, Multidisciplinary
Keshaba N. N. Parida, J. Narasimha Moorthy
Summary: Hypervalent iodine (III and V) compounds undergo positional isomerization via pseudorotation or twisting. By using steric hindrance, the twisting process can be facilitated to promote reactivity. Ortho-substitution in iodanes accelerates the alpha-tosyloxylation of ketones and oxidation of alcohols. The enhanced reactivity is a result of non-planarity induced by steric hindrance and the weakening of the 3c-4e bonds involving the hypervalent iodine atom. Ortho-substitution is an important strategy to control reactivity, selectivity, and develop new catalysts for various reactions. This review covers the literature developments on the effect of substituents and twisting/pseudorotation on the stability and reactivity of hypervalent iodanes and their application in synthetic transformations.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Carlee A. Montgomery, Islam Jameel, Fabio Cuzzucoli, Tristan Chidley, W. Scott Hopkins, Graham K. Murphy
Summary: The electrostatic potential energy maps of iodonium ylides were systematically evaluated for the first time, revealing the presence of two sigma-holes with differing electron deficiencies. In addition, a systematic evaluation of carboxylic acids, phenols and thiophenols in the O/S-alkylation reaction of iodonium ylides showed that only phenols with electron-withdrawing substituents were effective. This reaction, which involves halogen-bond activation of heteroatoms, complements existing diazo-based methods for alkylation of acidic functional groups and exhibits high yield and chemoselectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Editorial Material
Chemistry, Multidisciplinary
Avijit Roy, Martin Oestreich
Summary: For a long time, the Me3Si group has been difficult to manipulate into another useful functional group, but a hypervalent iodine reagent has now been shown to achieve electrophilic demethylation for this purpose. Coupled with the Tamao-Fleming oxidation, the Me3Si group can serve as a placeholder for a hydroxy group.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Durga Prasad Hari, Guillaume Pisella, Matthew D. Wodrich, Artem Tsymbal, Farzaneh Fadaei Tirani, Rosario Scopelliti, Jerome Waser
Summary: A new oxyalkynylation/cycloaddition reaction has been reported to synthesize complex polycyclic structures under mild conditions, with high efficiency and atom economy. The obtained products can be applied as chiral ligands for metal catalysis, providing a new method for organic synthesis. Computational studies provided a first rationalization of the low activation energy for the cycloaddition reaction based on counter-intuitive favorable dispersive interactions in the transition state.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Mira Kessler, Michael Kapiza, Stammler Hans-Georg, Beate Neumann, Roeschenthaler Gerd-Volker, Berthold Hoge
Summary: Phosphoranides with three phosphorus carbon bonds are rare in the literature. We synthesized these compounds using tris(pentafluoroethyl)phosphane, P(C2F5)(3), and cyanobis(pentafluoroethyl)phosphane, P(C2F5)(2)(CN), with electron withdrawing pentafluoroethyl groups. Metal fluorides MF (M=Ag, Cs) add to P(C2F5)(3) to yield M[P(C2F5)(3)F] salts, which subsequently undergo C2F4 loss to form M[P(C2F5)(2)F-2]. The cesium salt decomposes quickly at room temperature, while the silver salt decomposes slowly over several days. Ag[P(C2F5)(3)F] reacts with 2,2'-bipyridine to give [Ag(bipy){P(C2F5)(3)F}] for structural characterization. With P(C2F5)(2)(CN), AgF substitutes the cyano group instead of forming phosphoranides. However, [K(18-crown-6)]F adds to P(C2F5)(2)(CN) to yield [K(18-crown-6)][P(C2F5)(2)(CN)F], which can undergo substituent exchange to form [K(18-crown-6)][P(C2F5)(2)F-2] and possibly [K(18-crown-6)][P(C2F5)(2)(CN)(2)]. The equilibrium between the latter and [K(18-crown-6)]CN and P(C2F5)(2)(CN) favors the phosphane and cyanide salt.
Article
Chemistry, Multidisciplinary
Jiri Schulz, Ivana Cisarova, Robert Gyepes, Petr Stepnicka
Summary: In this study, Au-I complexes combining hard oxygen and soft (diphenylphosphanyl)ferrocene (L) ligands were synthesized and structurally characterized. Unique metal complexes were obtained, including a crown-like mixed-valent Au-0/Au-I cluster. N-bridged complexes were also prepared and further studied using DFT calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Pratiksha P. Gawas, Arbacheena Bora, Rence P. Reji, Buthanapalli Ramakrishna, Praveen B. Managutti, Christian R. Goeb, Sharmarke Mohamed, Yoshiyuki Kawazoe, Surya Velappa Jayaraman, Yuvaraj Sivalingam, Venkatramaiah Nutalapati
Summary: Tuning p-conjugation and varying functional units can enhance response behavior. Five donor-acceptor (D-A) molecular ensembles were developed with different electron-donating groups on 2-thiohydantoin (2TH) through C5 substitution. The influence of 2TH derivatives on surface interactions with volatile organic compounds (VOCs) was analyzed. The results demonstrate that electron-donating substituents-N(CH3)2 can improve sensing performance, while steric hindrance on the phenyl unit can modulate sensing performance.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Physical
Pratiksha P. Gawas, Arbacheena Bora, Rence P. Reji, Buthanapalli Ramakrishna, Praveen B. Managutti, Christian R. Goeb, Sharmarke Mohamed, Yoshiyuki Kawazoe, Surya Velappa Jayaraman, Yuvaraj Sivalingam, Venkatramaiah Nutalapati
Summary: Tuning the pi-conjugation and varying the functional units can enhance the response behavior towards VOCs. Five novel D-A molecular ensembles were developed by substituting C5 on 2-thiohydantoin with different electron-donating groups. The structure-property relationships were investigated through various analytical techniques. The results showed that electron-donating substituents can improve sensing performance by increasing electron density, while steric hindrance can modulate the performance.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Inorganic & Nuclear
Alexander Pocheim, Christoph Marschner, Judith Baumgartner
Summary: The reactions between rare-earth trichlorides and oligosilanylene diide in DME resulted in various new complexes, including the first examples of Si-La and Si-Pr compounds, as well as the first structurally characterized example of a Si-Dy complex. These complexes allow a systematic study of silyl rare-earth complexes through ligand exchange reactions while preserving the Si-RE interaction.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Preston R. Hoobler, Nery Villegas-Escobar, Justin M. Turney, Alejandro Toro-Labbe, Henry F. I. I. I. I. I. I. Schaefer
Summary: This research provides high-level ab initio geometries and energies for various aluminyl anions, including the simplest form and several substituted derivatives. Geometries were determined using advanced theoretical methods and energies were extrapolated to the complete basis set limit. The stability of these low-valent aluminum compounds and their potential industrial applications are discussed in terms of electrostatic, steric, orbital donation, back-donation, and stereoelectronic effects. The energetic analysis of the formation of each substituted anion is rationalized as the result of three energetic schemes, with the effectiveness of these schemes for determining relative formation energies being discussed.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Applied
Akira Yoshimura, Christopher D. Huss, Mackenzie Liebl, Gregory T. Rohde, Scott M. Larson, Gunnar B. Frahm, Mattew W. Luedtke, Tanner J. Schumacher, Zachary S. Gardner, Viktor V. Zhdankin, Pavel S. Postnikov, Mekhman S. Yusubov, Tsugio Kitamura, Akio Saito
Summary: Pseudocyclic beta-trifluorosulfonyloxy vinylbenziodoxolones were prepared and their structures were established by single crystal X-ray diffraction. The reaction of these compounds with azide anion led to beta-azido vinylbenziodoxolones, demonstrating vinylic nucleophilic substitution.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Zhen Lei, Jiao-Jiao Li, Zi-Ang Nan, Zhan-Guo Jiang, Quan-Ming Wang
Summary: The study introduces a novel cluster to cluster approach for assembling gold nanoclusters using preformed atomically precise Au-13 precursors, successfully synthesizing the well-known [Au-25(SR)(18)](-) magic cluster at high yield (overall yield close to 100%) and large scale (gram-scale based on gold). This method can be extended to the high-yield and large-scale synthesis of other metal nanoclusters.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Shang-Fu Yuan, Zhen Lei, Zong-Jie Guan, Quan-Ming Wang
Summary: A gold nanocluster with well-defined access has been successfully synthesized using a surface geometric mismatch strategy with mixed ligands. This cluster shows excellent performance in selective oxidation reactions and demonstrates good stability due to the protection of a negatively charged multidentate ligand.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Organic
Irina A. Mironova, Stefan F. Kirsch, Viktor V. Zhdankin, Akira Yoshimura, Mekhman S. Yusubov
Summary: This review summarizes recent approaches to the direct synthesis of organic azides using hypervalent iodine reagents. The first part discusses the use of unstable azidoiodinanes generated in situ, while the second part focuses on the application of stable azidobenziodoxoles as azidating reagents. The use of azidobenziodoxoles allows for selective direct azidation of specific bonds under mild reaction conditions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Environmental Sciences
Yi Wang, Anping Peng, Keqiang Ding, Lingxiao Ren, Zeyou Chen, Cheng Gu
Summary: This study explores the reaction of halophenols with Fe3+-montmorillonite and finds that the position and species of the substituents impact the reaction rate, product species, and transformation pathways. The results show that ortho-substituted chlorophenols are more reactive than meta-substituted chlorophenols, regardless of humidity. Bromophenols are slightly more reactive than chlorophenols and are more affected by humidity. Hydroxylated polyhalogenated diphenyl ethers are more frequently detected polymerization products.
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
Chemistry, Multidisciplinary
Florian Bachle, Achim Link, Abderrahmane Amgoune, Anis Tlili
Summary: The collaboration between Solvias and ICBMS has successfully designed air-stable Ni(H)/Josiphos complexes, which have been utilized as versatile precatalysts for diverse cross-coupling reactions. Their novel Ni-precatalysts enabled the development of challenging reactions, such as monoarylation of ammonia and alpha-arylation of acetone.
Article
Dentistry, Oral Surgery & Medicine
Yannick Coppel, Karim Nasr, Yann Prigent, Genevieve Gregoire
Summary: This study investigated the chemical and structural changes in dentin during the application of a mild universal adhesive. It was found that the etch-and-rinse mode led to a decrease in inorganic apatite and a reorganization of the mineral phase, while the self-etch mode formed a low amount of adhesive phosphate monoesters calcium salt. The adhesive had a similar interaction with dentin collagen in both modes, but the presence of isopropanol as the solvent significantly reduced the amount of free water molecules without significant changes in collagen structure.
Article
Chemistry, Physical
Hamid Ghorbani Shiraz, Zia Ullah Khan, Daniel Pere, Xianjie Liu, Yannick Coppel, Mats Fahlman, Magnus Berggren, Radoslaw Chmielowski, Myrtil L. Kahn, Mikhail Vagin, Xavier Crispin
Summary: Hydrogen technology, with its environmentally friendly and renewable properties, is considered a breakthrough for the energy industry. A recent study found that the bifunctional electrocatalyst TaS2 has high efficiency in both the hydrogen evolution reaction and the hydrogen oxidation reaction, and organic intercalation can inhibit the former. Intercalation is seen as a potential key strategy for tuning the performance of catalysts in this family.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
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
Chemistry, Multidisciplinary
Kevin Castello Lux, Katia Fajerwerg, Julie Hot, Erick Ringot, Alexandra Bertron, Vincent Colliere, Myrtil L. Kahn, Stephane Loridant, Yannick Coppel, Pierre Fau
Summary: This paper presents a new chemical method to improve the photocatalytic performance of WO3 nanoleaves by decorating them with a complementary metal oxide ZnWO4, thus enhancing the abatement of NO2 under UV exposure.
Article
Chemistry, Physical
Hamid Ghorbani Shiraz, Zia Ullah Khan, Daniel Pere, Xianjie Liu, Yannick Coppel, Mats Fahlman, Mikhail Vagin, Radoslaw Chmielowski, Myrtil L. Kahn, Magnus Berggren, Xavier Crispin
Summary: We investigated the effect of oxygen poisoning on the efficiency of hydrogen production and found that the oxygenated and intercalated electrocatalyst has a significantly lower exchange current density of the hydrogen evolution reaction compared to the pristine material.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Polymer Science
Fang Yin, Pascale Laborie, Barbara Lonetti, Yannick Coppel, Nancy Lauth-de Viguerie, Jean-Daniel Marty, Stephane Gineste
Summary: Doubly thermo-and pH-responsive PNIPAM-b-PDEAEAM polymers were synthesized by RAFT polymerization. The properties of these polymers and corresponding homopolymers in solution depend on pH and the protonation degree of the diethylamino moiety. The behavior of the polymers is also influenced by the nature of the polymer chain ends. At pH 10, both PNIPAM and PDEAEAM blocks contribute to phase transition and form stable spherical nanoobjects. At pH 4, PNIPAM-b-PDEAEAM with longer PDEAEAM length exhibits a two-step thermoresponsive behavior and forms large aggregates with a positively charged shell.
Article
Chemistry, Multidisciplinary
Omar Alami, Regis Laurent, Marine Tasse, Yannick Coppel, Jerome Bignon, Said El Kazzouli, Jean-Pierre Majoral, Nabil El Brahmi, Anne-Marie Caminade
Summary: In this study, two families of phosphorhydrazone dendrons were synthesized and characterized. These dendrons were then grafted onto graphene oxide (GO) via click reaction. The resulting materials were tested for their biological properties.
CHEMISTRY-A EUROPEAN JOURNAL
(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, Inorganic & Nuclear
Xinyu Yang, Alejandro Enriquez-Cabrera, Dorian Toha, Yannick Coppel, Lionel Salmon, Azzedine Bousseksou
Summary: A pure mixed-anion Fe(NH(2)trz)(3)(BF4)(SiF6)(0.5) spin crossover complex is obtained through a solid-liquid post synthetic modification approach from the Fe(NH(2)trz)(3)(BF4)(2) parent complex. Highly crystalline powder samples incorporating homogeneous micrometric (1 & mu;m long) rod-shaped particles can be achieved using this method. This compound exhibits an abrupt spin crossover behavior with a narrow (10 K) hysteresis loop centered just above room temperature (320 K), making it highly interesting for integration into various application devices.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Physical
Sasaline Salomon Sambou, Roman Hromov, Illia Ruzhylo, Hui Wang, Audrey Allandrieu, Cassandra Sabatier, Yannick Coppel, Jean-Claude Daran, Florence Gayet, Agnes Labande, Eric Manoury, Rinaldo Poli
Summary: An amphiphilic polymeric core-crosslinked micelle containing a catalyst rhodium(I) complex showed high activity in aqueous biphasic hydrogenation reactions and exhibited good recyclability.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Multidisciplinary
Yinping Wang, Yannick Coppel, Christine Lepetit, Jean-Daniel Marty, Christophe Mingotaud, Myrtil L. Kahn
Summary: This study elucidates the crucial role of amine surfactants in the controlled anisotropic growth of ZnO nanoparticles and their impact on the nature of molecular species in solution, as well as the dynamic behavior on the surface of the grown ZnO nanocrystals. The structuring influence of alkyl substituents on the nitrogen atom of amines strongly influences the formation of molecular species in the solution and the subsequent growth of ZnO nanocrystals. Surface dynamic behavior, particularly H-bonding, plays a predominant role in driving nanocrystal growth and morphology determination, highlighting the importance of weak surface interactions in nanoscience progress.
NANOSCALE ADVANCES
(2021)
Article
Chemistry, Multidisciplinary
Ionut-Tudor Moraru, Luis M. Martinez-Prieto, Yannick Coppel, Bruno Chaudret, Lucy Cusinato, Iker del Rosal, Romuald Poteau
Summary: The study demonstrates the formation of stable carbides during CO bond dissociation on small ruthenium nanoparticles through DFT calculations and solid state C-13 NMR techniques. The mechanistic investigations reveal that carbide formation via hydrogen-assisted hydroxymethylidyne pathways is exothermic and occurs at reasonable kinetic cost on standard sites of the RuNPs. The possible formation of mu(6) ruthenium carbides in the tip-B-5 site, as well as the rearrangement of surface metal atoms resulting in a pseudo-octahedral metal center on the NP surface, are novel outcomes of the DFT study.