Article
Chemistry, Multidisciplinary
Florian Lind, Armido Studer
Summary: Acylsilanes, a class of organosilicon compounds, have been gaining increased attention due to their ability to generate carbenes and their usefulness as reagents in organic synthesis. In this study, a novel and efficient route for the synthesis of acylsilanes was reported through alkene hydrosilylation. By using acylhydrosilanes as silylation reagents in rhodium catalyzed alkene hydrosilylations, a wide range of acylsilanes can be accessed in good to excellent yields under mild conditions with high functional group tolerance and atom economy.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Pradeep K. R. Panyam, Boshra Atwi, Felix Ziegler, Wolfgang Frey, Michal Nowakowski, Matthias Bauer, Michael R. Buchmeiser
Summary: Rh(I) NHC and Rh(III) Cp* NHC complexes were immobilized inside mesoporous SBA-15, showing different reactivity and selectivity, particularly for aliphatic alkynes. The immobilized catalysts in SBA-15 exhibited excellent selectivity in hydrosilylation reactions, attributed to the confinement effect generated during immobilization.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Agustin A. de la Fuente-Olvera, Franciso J. Ruiz-Mendoza, Jose M. Vasquez-Perez, Myriam Melendez-Rodriguez, Alejandro Alvarez-Hernandez, Veronica Salazar-Pereda, Daniel Mendoza-Espinosa
Summary: We report the synthesis and characterization of a novel series of rhodium(I) complexes supported by hydroxyl-functionalized 1,2,3-triazolylidenes. These complexes exhibit excellent catalytic activity in the hydrosilylation of terminal alkynes and the 1,4-addition of boronic acid to 2-cyclohexenone.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Unai Prieto, Susan Azpeitia, Eider San Sebastian, Zoraida Freixa, Maria A. Garralda, Miguel A. Huertos
Summary: The study reports the selective synthesis of linear silanes from remote alkenes using new silane-thioether bidentate proligands, which were found to affect the activity of tandem reactions depending on the size of the substituent. The isomerization process was identified as the rate-determining step in this catalytic transformation.
Article
Chemistry, Multidisciplinary
Sebastian Mummel, Felix Lederle, Eike G. Huebner, Jan C. Namyslo, Martin Nieger, Andreas Schmidt
Summary: Sydnone methides are rare compounds that can form pi-electron rich anionic N-heterocyclic carbenes and coordinate with various metals, while also undergoing C-C coupling reactions under specific catalysts. Studies have determined their electronic properties and NMR spectra.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Yu-Hao Huang, Yichen Wu, Zile Zhu, Sujuan Zheng, Zihang Ye, Qian Peng, Peng Wang
Summary: This study demonstrated an asymmetric synthesis method for monohydrosilanes via intramolecular hydrosilylation strategy, with high diastereo-, regio-, and enantioselectivities, including chiral oxasilacycles. The catalyst loading could be reduced to 0.1 mol %, making it one of the most efficient methods for accessing chiral monohydrosilanes. Mechanistic studies suggest a Chalk-Harrod mechanism for the Rh-catalyzed intramolecular asymmetric hydrosilylation reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Inorganic & Nuclear
Wenjing Yang, Qingqing Fan, Haiquan Yang, Hongjian Sun, Xiaoyan Li
Summary: The industrialization of alkene hydrosilylation catalyzed by cheap metals has attracted attention in recent years. In this study, a [P, C] chelate cobalt(I) complex was found to exhibit higher efficiency and selectivity in the hydrosilylation of alkenes compared to its cobalt(III) counterpart. The catalytic system demonstrated 100% Markovnikov selectivity for aromatic alkenes and almost 100% anti-Markovnikov selectivity for aliphatic alkenes.
Article
Chemistry, Multidisciplinary
Luisa Leinauer, Giorgio Parla, Julian Messelbeger, Alberto Herrera, Frank W. Heinemann, Jens Langer, Ilya Chuchelkin, Alexander Grasruck, Sibylle Friess, Ahmed Chelouan, Konstantin Gavrilov, Romano Dorta
Summary: Alkene planar chirality is introduced in the 'privileged' P-alkene phosphoramidite ligand, resulting in optically pure complexes of Rh(i) and Pd(ii). These complexes catalyze conjugate additions of boron C-nucleophiles to enones and allylic alkylations, respectively. The planar chirality of the alkene exhibits absolute enantiocontrol over the BINOL auxiliary in the Rh-catalyzed reaction.
CHEMICAL COMMUNICATIONS
(2023)
Editorial Material
Chemistry, Multidisciplinary
Roman Franz, Sina Nasemann, Clemens Bruhn, Zsolt Kelemen, Rudolf Pietschnig
Summary: Tert-butyl-substituted diphospha[2]ferrocenophane was used as a stereochemically confined diphosphane to explore the addition of O, S, Se, and Te. Intermediates during rearrangement point to a disproportionation/synproportionation mechanism for the S and Se derivatives. Cyclic voltammetry and DFT studies indicate ferrocene-centred oxidation for most of the compounds presented.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Yan Yan, Jiayun Li, Ying Bai, Jiajian Peng
Summary: A series of polyethylene glycol phosphine ligands with N donor were synthesized and coordinated with Co(BF4)2 to catalyze the hydrosilylation of olefins and silanes. The best catalytic effect was achieved when the amount of catalyst was 0.5 mol% and the temperature was 90 degrees C with a reaction time of 5 hours. The catalytic cycle performance was also studied, and it was found that after 8 times, its yield could still reach> 90%.
ARABIAN JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Hannah K. Wagner, Hubert Wadepohl, Joachim Ballmann
Summary: A metal-templated synthetic route to cyclic (aryl)(ylidic) mesoionic carbenes (CArY-MICs) with an endocyclic P-ylide is presented. This approach allows controlled cyclisation of a P,P'-diisopropyl-substituted 2,2'-diphosphinotolane and formation of chelate complexes coordinated by a phosphine donor and the CArY-MIC carbon atom. The reversible formation of P-C bonds in the presence of a third fac-positioned open coordination site was demonstrated in molybdenum complexes.
Article
Chemistry, Multidisciplinary
Roman Franz, Sina Nasemann, Clemens Bruhn, Zsolt Kelemen, Rudolf Pietschnig
Summary: Stereochemically confined tert-butyl-substituted diphospha[2]ferrocenophane has been used to explore the addition of O, S, Se and Te, revealing a rearrangement mechanism that has been tracked through NMR spectroscopy and DFT calculations. Experimental results show a ferrocene-centred oxidation for most compounds.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Inorganic & Nuclear
Jennifer L. Minnick, John Raincrow, Grace Meinders, Reza Latifi, Laleh Tahsini
Summary: Six new Cu(I) complexes with pincer ligands have been synthesized and characterized. The study reveals that the structure, copper nuclearity, and redox properties of the complexes are influenced by the electronic effects induced by the aryl wingtips.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
Raphael H. Lam, Sinead T. Keaveney, Barbara A. Messerle, Indrek Pernik
Summary: In order to investigate the access to bimetallic catalysts with better performance than their monometallic analogues, rhodium(I) complexes with mono- and bimetallic NHC/phosphine (NHC = N-heterocyclic carbene) ligands were designed, synthesized, and characterized. These complexes were used as catalysts for the intermolecular hydrosilylation of diphenylacetylene. All four catalysts showed significantly higher catalytic rates than the donor ligands. The bimetallic catalyst design resulted in enhanced catalytic activity compared to the monometallic analogue. The degree of bimetallic enhancement was found to be highly dependent on reaction conditions, coligands used, and substrate addition order, as revealed by data and mechanistic studies.
Article
Chemistry, Physical
Raphael H. Lam, Sinead T. Keaveney, Barbara A. Messerle, Indrek Pernik
Summary: In this study, mono- and bimetallic NHC/phosphine-ligated rhodium(I) complexes were designed, synthesized, and characterized as catalysts for the intermolecular hydrosilylation of diphenylacetylene. All four catalysts exhibited significantly faster catalytic rates than the donor ligands. The bimetallic catalyst design resulted in enhanced catalytic activity compared to the monometallic analogue. The degree of bimetallic enhancement was found to depend on reaction conditions, coligands used, and the substrate addition order, as revealed by data analysis and mechanistic studies.
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, Multidisciplinary
Julian Sobieski, Illia Ruzhylo, Grzegorz Szczepaniak, Adam Gorczynski, Krzysztof Matyjaszewski, Eric Manoury, Rinaldo Poli
Summary: Simple synthetic routes for the regioselective deuteration of tris[2-(dimethylamino)ethyl]amine (Me6TREN) variants are described. Formation of imine with formaldehyde-d(2) from tris(2-aminoethyl)amine (TREN) and subsequent reduction with NaBD4 resulted in N[CH2CH2N(CD3)(2)](3) or d(18)-Me6TREN in 79% yield. A trisubstitution protocol from 2-bromo-N,N-dimethylacetamide and ammonium carbonate, followed by reduction of the N(CH2CONMe2)(3) intermediate with lithium aluminum deuteride, afforded N[CH2CD2N(CH3)(2)](3) or (d(6)-arm)-Me6TREN in three steps and 52% overall yield. A similar protocol using 2-bromo-N,N-dimethyl-d(2)-acetamide, obtained from d(4)-acetic acid in two steps, and reduction of the N(CD2CONMe2)(3) intermediate with lithium aluminum hydride, resulted in N[CD2CH2N(CH3)(2)](3) or (d(6)-cap)-Me6TREN in four steps and 13% overall yield.
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
Chemistry, Inorganic & Nuclear
Ambra Maria Fiore, Valentina Petrelli, Christophe Fliedel, Eric Manoury, Piero Mastrorilli, Rinaldo Poli
Summary: The solution behavior of complex [Rh(COD)(& mu;-OAc)](2) in dichloromethane has been investigated in the absence and presence of PPN+OAc- using multinuclear NMR spectroscopy. The addition of PPN+OAc- results in the generation of [Rh(COD)(OAc)(2)](-) through equilibration. Rapid exchange between different Rh complexes and acetate ligands is observed at room temperature, but freezing the exchange at lower temperatures allows for the coalescence of certain NMR resonances.
DALTON TRANSACTIONS
(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)
