Article
Chemistry, Inorganic & Nuclear
Daniel Martinez-Martinez, M. Leon Santiago, Ruben A. Toscano, Manuel Amezquita-Valencia
Summary: A series of pyridylimine ligands with variations of the substituent at the imine nitrogen were synthesized and coordinated to the [MoCl2O2] core. The novel complexes showed excellent catalytic activity and fine selectivity in the epoxidation reaction, with complex [MoCl2O2(L)] (L: N-(2-Pyridinylmethylene)-1-tert-butylimine) C-5 being the best catalytic precursor.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Alexandra Walter, Wolfgang Eisenreich, Golo Storch
Summary: This study reports a photochemical approach using flavin catalysts to oxidize silyl enol ethers to α,β-unsaturated ketones. The catalysts exhibit good stability throughout the reaction and can be successfully applied in subsequent aerobic epoxidation reactions. The sequential catalytic activity of flavin enables rapid diversification of substrates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Silvija Mrkonja, Edi Topic, Mirna Mandaric, Dominique Agustin, Jana Pisk
Summary: Molybdenum compounds containing benzaldehyde-based hydrazones were synthesized and studied for their solid-state structures. These compounds were utilized as catalysts for cyclooctene epoxidation, showing high activity and selectivity under different conditions.
Review
Chemistry, Inorganic & Nuclear
Sofia M. Bruno, Anabela A. Valente, Isabel S. Goncalves, Martyn Pillinger
Summary: The metal-catalyzed epoxidation of olefins using molybdenum complexes as catalysts has been extensively studied. This review provides a comprehensive analysis of the use of group 6 hexacarbonyls as precursors and heteroleptic complexes for olefin epoxidation, covering topics such as precursor synthesis, catalyst activation, and mechanistic studies.
COORDINATION CHEMISTRY REVIEWS
(2023)
Article
Chemistry, Multidisciplinary
George Dhimba, Alfred Muller, Koop Lammertsma
Summary: This study investigates the mechanisms of ligand rearrangement in octahedral chiral-at-metal complexes. The lowest energy cis isomer and its interconversion with other isomers are calculated. The connectivity of all enantiomeric minima and transition structures is summarized, and the influence of N-substitution on the favored pathway is evaluated.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
Emmanuel D. Silva, Otavio A. L. Alves, Rogerio T. Ribeiro, Rafael C. R. Chagas, Jose A. F. P. Villar, Jefferson L. Princival
Summary: A new base-and halogen-free homogeneous oxidation system was developed in this study, aiming to selectively oxidize allyl, furyl, aryl, and heteroaryl primary alcohols. The system uses CuCl2/TMEDA/TEMPO with mild reaction conditions to produce aldehydes in high yields, and TMEDA as a ligand significantly affects the redox potential in the system.
APPLIED CATALYSIS A-GENERAL
(2021)
Review
Chemistry, Multidisciplinary
Justus Diekamp, Thomas Seidensticker
Summary: The recycling of homogeneous catalysts in a homogeneous matrix is a challenging task for many reactions aiming for industrial applications. Although various synthetic approaches for recyclable homogeneous catalysts exist, a concise overview of catalyst modifications is lacking in the literature. This review aims to fill this gap by summarizing the existing synthesis pathways for polar, non-polar, fluorous, and molecular-weight-enlarged catalysts and examining their modular and late-stage approaches. Additionally, the potential for a generally applicable tag library to facilitate catalyst modifications for specific recycling strategies is explored.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Niklas F. Both, Anke Spannenberg, Haijun Jiao, Kathrin Junge, Matthias Beller
Summary: The use of bis(NHC) manganese(I) complexes 3 as catalysts for the hydrogenation of esters was investigated. Various aromatic and aliphatic esters were successfully hydrogenated at mild temperatures and low catalyst loadings using complexes 3 with KHBEt3 as additive, highlighting the efficiency of the novel catalytic system. Additionally, the versatility of the developed catalytic system was demonstrated by the hydrogenation of other substrate classes like ketones, nitriles, N-heteroarenes, and alkenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Francis Bru, Mathieu Lesieur, Albert Poater, Alexandra M. Z. Slawin, Luigi Cavallo, Catherine S. J. Cazin
Summary: The synthesis and isolation of [Pd(NHC)(PhC equivalent to CPh)] complexes were reported, which are new 14-electron Pd(0)-complexes that serve as key synthons for known palladium(0) and palladium(II) species and allow access to unprecedented mixed NHC-phosphite palladium(0) complexes. These complexes are also capable of catalyzing the facile hydrosilylation of allenes. DFT calculations provided insights into the relatively weak interaction between the metal and the diphenylacetylene ligand, comparing it with other ligands with varying coordinating power, structure, and electronic properties.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Huelya Avci oezbek, Funda Demirhan
Summary: A method for the epoxidation of cis-cyclooctene using Lindqvist type POMs Cp*2MoxW6-xO17 (x=0, 2, 4, 6) and [Cp*MoxW6-xO18](-) as catalysts and 30% H2O2 as a green oxidant was studied. This catalytic system showed excellent yields for cis-cyclooctene in acetonitrile at 55 °C. The highest epoxidation efficiency of 99% was achieved under optimized conditions using Ph4P[Cp*MoW5O18] (2c).
Review
Chemistry, Multidisciplinary
Nadim Ayoub, Joumana Toufaily, Erwann Guenin, Gerald Enderlin
Summary: Lignocellulosic feedstocks can be used to generate biofuels and biochemicals, but methods using metal catalysts have some issues. This Review summarizes catalytic methods using metal and metal-free catalysts for oxidation reactions and demonstrates the potential of metal-free catalysts.
Article
Chemistry, Physical
Madeleine A. Ehweiner, Fabian Wiedemaier, Bassam Lajin, Joerg A. Schachner, Ferdinand Belaj, Walter Goessler, Nadia C. Moesch-Zanetti
Summary: Two molybdenum(VI) complexes act as catalysts for the reduction of (per)chlorate, with the pyrimidine-2-thiolate system showing higher efficiency. The reduction of (per)chlorate to chloride is facilitated by the catalysts, with the initial oxygen atom transfer from [MoO2L2] to PPh3 being the rate-determining step.
Article
Chemistry, Organic
Francesco Messa, Andrea Nicola Paparella, Dominik Vesely, Jozef Krajcovic, Paride Papadia, Serena Perrone, Antonio Salomone
Summary: The Pd-catalyzed amino- and alkoxycarbonylation of aryl iodides has been successfully carried out in a bioinspired Deep Eutectic Solvent and under gas-free conditions using Mo(CO)(6) as the CO source. This method provides a high-yielding (up to 99%) and efficient synthesis of carboxylic amides and esters in a short reaction time (2 h) and under mild reaction conditions (80 degrees C) with a low catalyst loading (2.5 mol %).
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Sarah E. Jenny, Juan M. Serviano, Ainara Nova, Graham E. Dobereiner
Summary: This study proposes a reaction pathway for a precatalyst that exhibits high Z selectivity in alkene isomerization. Computational modeling suggests that the isomerization occurs through an allyl hydride shift mechanism, where hydride migration from one position to another takes place. This is the first study to propose such a hydride migration mechanism in alkene isomerization.
Article
Chemistry, Multidisciplinary
Jana-Alina Zur, Michelle Schmidt, Kai-Stephan Feichtner, Prakash Duari, Julian Loffler, Thorsten Scherpf, Viktoria H. Gessner
Summary: This study reports the formation of stable PH ylides and their ability to promote the formation of carbanionic phosphines with strong donor abilities and high basicities. Additionally, they can form zwitterionic complexes and be used for catalytic hydroamination reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Dimitri Berne, Sebastien Lemouzy, Pascale Guiffrey, Sylvain Caillol, Vincent Ladmiral, Eric Manoury, Rinaldo Poli, Eric Leclerc
Summary: This study describes a spontaneous (uncatalyzed) Michael addition of thiols to alpha-trifluoromethyl acrylates and its efficient application in the preparation of a thermoset. Mechanistic investigation reveals a probable solvent-assisted proton transfer in the rate-determining step and a considerable lowering of the energy barrier induced by the CF3 group in the addition of arene- and alkanethiols to tert-butyl trifluoromethyl acrylate in polar aprotic solvents.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Paven Kisten, Eric Manoury, Agusti Lledos, Adrian C. Whitwood, Jason M. Lynam, John M. Slattery, Simon B. Duckett, Rinaldo Poli
Summary: The reaction between [IrCl(COD)](2) and dppe in a 1 : 2 ratio was studied under different conditions. The formation of [IrCl(COD)(dppe)], 1, was observed at room temperature without base. In the presence of a strong base, hydride complexes and deprotonation reactions were observed, leading to the formation of various complexes such as [IrH(1,2,5,6-eta(2):eta(2)-COD)(dppe)], [IrH(1-kappa-4,5,6-eta(3)-C8H12)(dppe)], and [IrH(1-kappa-4,5,6-eta(3)-C8H10)(dppe)]. The selectivity and mechanism of these reactions were explained using DFT calculations.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Maxime Michelas, Yasmine K. Redjel, Meriem Benslimane, Rinaldo Poli, Christophe Fliedel
Summary: This study reports the synthesis and characterization of cobalt(II) and acetato cobalt(III) complexes with tripodal tetradentate diamino-bis(phenolate) ligands. The structures of the proligand and complexes were determined by X-ray crystallography. The complexes exhibited different coordination modes and were not efficient initiators or moderators for radical polymerization reactions.
INORGANICA CHIMICA ACTA
(2023)
Article
Chemistry, Physical
Josipa Sarjanovic, Martina Stojic, Mirta Rubcic, Luka Pavic, Jana Pisk
Summary: Molybdenum coordination complexes with biological and pharmacological potential and good catalytic performance were synthesized using a hydrazone Schiff-base tetradentate ligand. The structures of the ligands and complexes were determined by spectroscopic methods and X-ray diffraction. The electrical properties of the complexes were examined using impedance spectroscopy.
Article
Polymer Science
Jirong Wang, Chi Zhang, Yong Zhang, Gong Chen, Rinaldo Poli, Xiaolin Xie, Zhigang Xue
Summary: A simple aza-Michael addition method induced by lithium salts is used to design and fabricate high-performance polymer electrolytes with a more amorphous cross-linked structure. The in situ-constructed gel polymer electrolyte exhibits high ionic conductivity and excellent interface stability with the electrodes, leading to a LiFePO4 battery with high initial specific discharge capacity and good rate performance.
Article
Chemistry, Multidisciplinary
Abdelhak Lachguar, Uchchhal Bandyopadhyay, Mehdi Ech-Chariy, Sandrine Vincendeau, Catherine Audin, Jean-Claude Daran, Eric Manoury, Rinaldo Poli, Eric Deydier
Summary: This study presents a new solvent-less reaction method to convert benzylic, allylic, ferrocenyl or tertiary alcohols into S-thioesters, which are stable precursors of corresponding thiols. The reaction involves reactions in neat thioacetic acid in the presence of tetrafluoroboric acid, and increasing the HBF4 concentration can enhance the reaction rate. Control experiments and DFT calculations provide insights into the mechanism of the reaction and the formation of intermediate products.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Chemistry, Inorganic & Nuclear
Meenu Murali, Eric Manoury, Rinaldo Poli
Summary: This review introduces various types of CooANs according to the nature of the metal-binding functions and discusses the mechanism of crosslink migration. CooANs can be obtained by the combination of ligand-functionalized polymers and metal ions or clusters, with crosslink migration occurring through ligand exchange with available free ligands in the polymer matrix.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Polymer Science
Dimitri Berne, Rinaldo Poli, Sylvain Caillol, Vincent Ladmiral, Eric Leclerc
Summary: This study develops a series of catalyst-free covalent adaptable networks (CANs) using a reversible thia-Michael reaction. By modulating the structure and functionality of the thiol monomers, a wide range of mechanical and thermal properties are achieved. The study also highlights the relationship between monomer structure and dynamic properties, and evaluates the reprocessing capability of the materials.
Article
Polymer Science
Julian Sobieski, Sajjad Dadashi Silab, Lucas Thevenin, Krzysztof Matyjaszewski, Christophe Fliedel, Rinaldo Poli
Summary: The termination processes of the tertiary carbomethoxyisopropylradical, (COOMe)Me2C & BULL;, were investigated by H-1 NMR. The investigation assessed the contributions of the Cu-I/L-catalyzed radical termination (CRT) and the reductive radical termination (RRT) to the spontaneous bimolecular radical terminations (RT). It also reassessed the product distribution for the RT of the diffused and caged radicals obtained from the thermal activation of V-601.
Article
Chemistry, Inorganic & Nuclear
Rinaldo Poli, Dung Nguyen, Yu-Sheng Liu, Eva Harth
Summary: This work investigated the thermal switchability of ethylene coordination/insertion to controlled radical polymerization of methyl acrylate using Brookhart-type α-diimine Pd-II catalysts. The impact of bulky α-diimine N-substituents was explored, revealing the reversible activation of the Pd-II-C bond and trapping during radical MA polymerization. DFT calculations evaluated the sterics effect on the stability of PE-MA-Pd-II chain-end structures and the bond dissociation-free energy for Pd(II)-C bond cleavage. Experimental investigations showed the failure of the Pd-II system to control radical polymerization of MA through OMRP mechanism.
Article
Materials Science, Multidisciplinary
D. Bhadrarao, L. Pavic, A. Bafti, J. Pisk, A. Venkata Sekhar, G. Naga Koti Reddy, V. Ravi Kumar, G. Sahaya Baskaran, G. Naga Raju, N. Veeraiah
Summary: In this study, the dielectric properties of PBB glass ceramics doped with varying CuO concentrations were investigated. The structural analysis revealed the presence of anisotropic CuBi2O4 ferroelectric crystal phases in these glass ceramics. The study found that the CuO content affects the dielectric properties, and an appropriate CuO concentration can enhance the conductivity of the material.
ECS JOURNAL OF SOLID STATE SCIENCE AND TECHNOLOGY
(2023)
Article
Chemistry, Inorganic & Nuclear
Maxime Michelas, Jean-Claude Daran, Alix Sournia-Saquet, Christophe Fliedel, Rinaldo Poli
Summary: The addition of benzoyl peroxide to [Co-II(acac)(2)] selectively produces [Co-III(acac)(2)(O2CPh)], a mononuclear Co-III complex with an octahedral coordination geometry. This compound can serve as a thermal initiator for radical polymerisation. Addition of ligands (L = py, NEt3) induces chelate ring opening and formation of different isomers. The addition of py strengthens the Co-III-O2CPh bond and lowers the initiator efficiency, while the addition of NEt3 quenches the benzoate radical.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Illia Ruzhylo, Sandrine Vincendeau, Philippe Dauban, Eric Manoury, Rinaldo Poli, Agnes Labande
Summary: A series of heteroleptic dirhodium(ii) complexes have been evaluated for the redox-responsive decomposition of diazo substrates prone to chemoselectivity issues. The counter-anion of oxidized ferrocenyl-containing complexes was found to influence the chemoselectivity, with SbF6- and BAr4F- resulting in greater differences compared to BF4-. The correlation between ferrocenyl substituents and chemoselectivity switch was not obvious, but introducing a saturated tether drastically decreased the difference. Changing the electronic properties of only one ligand on dirhodium, by oxidation of its ferrocenyl part, had a marked influence on reaction selectivity.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Chantal J. Abou-Fayssal, Christophe Fliedel, Rinaldo Poli, Anders Riisager, Karine Philippot, Eric Manoury
Summary: This study introduces a method to improve the confinement of rhodium nanoparticles (RhNPs) in nanoreactors by introducing phosphine oxide as anchoring groups in the hydrophobic core of amphiphilic star-block copolymers. The RhNP-loaded latex exhibits excellent catalytic activity and recyclability, making it a promising candidate for aqueous biphasic catalysis.
MATERIALS TODAY CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Pardeep Dahiya, Nidhi Garg, Rinaldo Poli, Basker Sundararaju
Summary: To achieve the goal of a carbon-free energy economy, a well-defined air-stable Cp*Co(III) catalyst has been developed for the transfer hydrogenation of quinoline derivatives and the oxidative dehydrogenation of cyclic amines in water. These findings provide new avenues for studying environmentally benign cobalt catalysts for hydrogenation and dehydrogenation reactions.
DALTON TRANSACTIONS
(2023)
