21 results on '"Maxime, Tricoire"'
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2. Frontispiece: Molecular Lanthanide Switches for Magnetism and Photoluminescence
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Luca Münzfeld, Milena Dahlen, Adrian Hauser, Nolwenn Mahieu, Senthil Kumar Kuppusamy, Jules Moutet, Maxime Tricoire, Ralf Köppe, Léo La Droitte, Olivier Cador, Boris Le Guennic, Grégory Nocton, Eufemio Moreno‐Pineda, Mario Ruben, and Peter W. Roesky more...
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General Chemistry ,Catalysis - Published
- 2023
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Catalog
3. Molecular Lanthanide Switches for Magnetism and Photoluminescence
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Luca Münzfeld, Milena Dahlen, Adrian Hauser, Nolwenn Mahieu, Senthil Kumar Kuppusamy, Jules Moutet, Maxime Tricoire, Ralf Köppe, Léo La Droitte, Olivier Cador, Boris Le Guennic, Grégory Nocton, Eufemio Moreno‐Pineda, Mario Ruben, Peter W. Roesky, Karlsruher Institut für Technologie (KIT), Institut Polytechnique de Paris (IP Paris), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universidad de Panamá (UP), KIT is acknowledged for financial support. MD thanks the Fonds der Chemischen Industriefor the generous fellowship (No. 103581). AH, MR, and PR gratefully acknowledge financial support from the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) through the Collaborative Research Centre \'4f for Future\' (CRC 1573, project number 471424360) projects C1 and B2. E.M.-P. thanks the Panamanian National System of Investigators (SNI, SENACYT) and SENACYT (project PFID-FID-2021-60) for support. Parts of this work have received funding from the ERC under grant agreement No 716314 and from an ANR (French National Research Agency) granted collaborative project (ANR-19-CE07-0019-1). CNRS and Ecole polytechnique are thanked for financial support. NM thanks ENS Paris-Saclay., and ANR-19-CE07-0019,RelaxMax,Complexes organométalliques de lanthanides à relaxation magnétique lente(2019) more...
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Chemistry & allied sciences ,Magnetism ,Sandwich Compounds ,General Chemistry ,General Medicine ,Lanthanides ,Catalysis ,Molecular switches ,Sandwich compounds ,ddc:540 ,[CHIM]Chemical Sciences ,Photoluminescence ,Molecular Switches - Abstract
Solvation of [(CNT)Ln(η$^8$-COT)] (Ln=La, Ce, Nd, Tb, Er; CNT=cyclononatetraenyl, i.e., C$_9$H$_9$−; COT=cyclooctatetraendiid, i.e., C$_8$H$_8$$^2−$) complexes with tetrahydrofuran (THF) gives rise to neutral [(η$^4$-CNT)Ln(thf)$_2$(η$^8$-COT)] (Ln=La, Ce) and ionic [Ln(thf)$_x$(η$^8$-COT)][CNT] (x=4 (Ce, Nd, Tb), 3 (Er)) species in a solid-to-solid transformation. Due to the severe distortion of the ligand sphere upon solvation, these species act as switchable luminophores and single-molecule magnets. The desolvation of the coordinated solvents can be triggered by applying a dynamic vacuum, as well as a temperature gradient stimulus. Raman spectroscopic investigations revealed fast and fully reversible solvation and desolvation processes. Moreover, we also show that a Nd:YAG laser can induce the necessary temperature gradient for a self-sufficient switching process of the Ce(III) analogue in a spatially resolved manner. more...
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- 2023
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4. Multitier Diversification in Web-Based Software Applications.
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Simon Allier, Olivier Barais, Benoit Baudry, Johann Bourcier, Erwan Daubert, Franck Fleurey, Martin Monperrus, Hui Song, and Maxime Tricoire
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- 2015
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5. Reactive Heterobimetallic Complex Combining Divalent Ytterbium and Dimethyl Nickel Fragments
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Ding Wang, Jules Moutet, Maxime Tricoire, Marie Cordier, and Grégory Nocton
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divalent lanthanides ,redox non-innocent ligand ,magnetism ,CO insertion ,Inorganic chemistry ,QD146-197 - Abstract
This article presented the synthesis and characterization of original heterobimetallic species combining a divalent lanthanide fragment and a divalent nickel center bridged by the bipyrimidine ligand, a redox-active ligand. X-ray crystal structures were obtained for the Ni monomer (bipym)NiMe2, 1, as well as the heterobimetallic dimer compounds, Cp*2Yb(bipym)NiMe2, 2, along with 1H solution NMR, solid-state magnetic data, and DFT calculations only for 1. The reactivity with CO was investigated on both compounds and the stoichiometric acetone formation is discussed based on kinetic and mechanistic studies. The key role of the lanthanide fragment was demonstrated by the relatively slow CO migratory insertion step, which indicated the stability of the intermediate. more...
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- 2019
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6. Electron Shuttle in
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Maxime, Tricoire, Ding, Wang, Thayalan, Rajeshkumar, Laurent, Maron, Grégory, Danoun, and Grégory, Nocton
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Simple
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- 2022
7. Electron Shuttle in N-Heteroaromatic Ni Catalysts for Alkene Isomerization
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Maxime Tricoire, Ding Wang, Thayalan Rajeshkumar, Laurent Maron, Grégory Danoun, Grégory Nocton, Laboratoire de chimie moléculaire (LCM), École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS) more...
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nickel ,catalysis ,[CHIM.ORGA]Chemical Sciences/Organic chemistry ,redox-active ligand ,[CHIM.COOR]Chemical Sciences/Coordination chemistry ,[CHIM.CATA]Chemical Sciences/Catalysis ,alkene isomerization ,heterometallic complexes - Abstract
International audience; Simple N-heteroaromatic Ni(II) precatalysts, (L)NiMe2 (L = bipy, bipym), were used for alkene isomerization. With an original reduction method using a simple borane (HB(Cat)), a low-valent Ni center was formed readily and showed good conversion when a reducing divalent lanthanide fragment, Cp*2Yb, was coordinated to the (bipym)NiMe2 complex, a performance not achieved by the monometallic (bipy)NiMe2 analogue. Experimental mechanistic investigations and computational studies revealed that the redox non-innocence of the L ligand triggered an electron shuttle process, allowing the elusive formation of Ni(I) species that were central to the isomerization process. Additionally, the reaction occurred with a preference for mono-isomerization rather than chain-walking isomerization. The presence of the low-valent ytterbium fragment, which contributed to the formation of the electron shuttle, strongly stabilized the catalysts, allowing catalytic loading as low as 0.5%. A series of alkenes with various architectures have been tested. The possibility to easily tune the various components of the heterobimetallic catalyst reported here, the ligand L and the divalent lanthanide fragment, opens perspectives for further applications in catalysis induced by Ni(I) species. more...
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- 2022
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8. Correction to 'Electron Shuttle in N-Heteroaromatic Ni Catalysts for Alkene Isomerization'
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Maxime Tricoire, Ding Wang, Thayalan Rajeshkumar, Laurent Maron, Grégory Danoun, and Grégory Nocton
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- 2022
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9. Size-Controlled Hapticity Switching in [Ln(C
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Maxime, Tricoire, Luca, Münzfeld, Jules, Moutet, Nolwenn, Mahieu, Léo, La Droitte, Eufemio, Moreno-Pineda, Frédéric, Gendron, Jeremy D, Hilgar, Jeffrey D, Rinehart, Mario, Ruben, Boris, Le Guennic, Olivier, Cador, Peter W, Roesky, and Grégory, Nocton more...
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single molecule magnets ,Full Paper ,magnetism ,Hot Paper ,cyclononatetraenyl ,lanthanides ,Full Papers ,organometallics - Abstract
Sandwich complexes of lanthanides have recently attracted a considerable amount of interest due to their applications as Single Molecule Magnet (SMM). Herein, a comprehensive series of heteroleptic lanthanide sandwich complexes ligated by the cyclononatetraenyl (Cnt) and the cyclooctatetraenyl (Cot) ligand [Ln(Cot)(Cnt)] (Ln=Tb, Dy, Er, Ho, Yb, and Lu) is reported. The coordination behavior of the Cnt ligand has been investigated along the series and shows different coordination patterns in the solid‐state depending on the size of the corresponding lanthanide ion without altering its overall anisotropy. Besides the characterization in the solid state by single‐crystal X‐ray diffraction and in solution by 1H NMR, static magnetic studies and ab initio computational studies were performed., A series of trivalent lanthanide heteroleptic sandwich complexes with the cyclooctatetraenyl (Cot) and cyclononatetraenyl (Cnt) ligands shows a significant bending of the Cnt ligand when the size of the ion decreases, implying a size‐controlled hapticity switch. more...
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- 2021
10. Frontispiece: Intermediate Valence States in Lanthanide Compounds
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Maxime Tricoire, Thomas Simler, Nolwenn Mahieu, and Grégory Nocton
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Lanthanide ,Crystallography ,Valence (chemistry) ,Chemistry ,Organic Chemistry ,General Chemistry ,Spectroscopy ,Catalysis - Published
- 2021
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11. Intermediate Valence States in Lanthanide Compounds
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Nolwenn Mahieu, Grégory Nocton, Maxime Tricoire, Thomas Simler, Laboratoire de chimie moléculaire (LCM), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X) more...
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Lanthanide ,spectroscopy ,Valence (chemistry) ,010405 organic chemistry ,Chemistry ,Organic Chemistry ,theoretical computations ,Theoretical models ,General Chemistry ,010402 general chemistry ,01 natural sciences ,Catalysis ,Article ,0104 chemical sciences ,Chemical physics ,intermediate valence ,Electronic effect ,[CHIM]Chemical Sciences ,lanthanides ,Spectroscopy ,organometallics - Abstract
Over more than 50 years, intermediate valence states in lanthanide compounds have often resulted in unexpected or puzzling spectroscopic and magnetic properties. Such experimental singularities could not be rationalised until new theoretical models involving multiconfigurational electronic ground states were established. In this minireview, the different singularities that have been observed among lanthanide complexes are highlighted, the models used to rationalise them are detailed and how such electronic effects may be adjusted depending on energy and symmetry considerations is considered. Understanding and tuning the ground-state multiconfigurational behaviour in lanthanide complexes may open new doors to modular and unusual reactivities. more...
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- 2020
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12. Bis-cyclooctatetraenyl Thulium(II): Highly Reducing Lanthanide Sandwich Single Molecule Magnets
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Léo La Droitte, Boris Le Guennic, Thomas Simler, Grégory Nocton, jules Schleinitz, Frédéric Gendron, Maxime Tricoire, Jules Moutet, Olivier Cador, and Carine Clavaguéra
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chemistry.chemical_classification ,Lanthanide ,Crystallography ,Electron transfer ,Materials science ,Thulium ,chemistry ,Ligand ,chemistry.chemical_element ,Molecule ,Single-molecule magnet ,Small molecule ,Divalent - Abstract
Divalent lanthanide organometallics are well known highly reducing compounds usually used for single electron transfer reactivity and small molecule activation. Thus, their very reactive nature prevented for many years the study of their physical properties, such as magnetic studies on a reliable basis. In this article, the access to rare organometallic sandwich compounds of TmII with the cyclooctatetraenyl (Cot) ligand impacts on the use of divalent organolanthanide compounds as an additional strategy for the design of performing Single Molecule Magnets (SMM). Herein, the first divalent thulium sandwich complex with f13 configuration behaving as a Single Molecule Magnet in absence of DC field is highlighted. more...
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- 2020
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13. Tridentate NNN Ligand Associating Amidoquinoline and Iminophosphorane: Synthesis and Coordination to Pd and Ni Centers
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Louis Mazaud, Marie Cordier, Audrey Auffrant, Maxime Tricoire, Sophie Bourcier, Vincent Gandon, Laboratoire de chimie moléculaire (LCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), and Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC) more...
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010405 organic chemistry ,Ligand ,Organic Chemistry ,Substituent ,chemistry.chemical_element ,010402 general chemistry ,01 natural sciences ,Medicinal chemistry ,0104 chemical sciences ,Inorganic Chemistry ,chemistry.chemical_compound ,Nickel ,chemistry ,Physical and Theoretical Chemistry ,[CHIM.OTHE]Chemical Sciences/Other - Abstract
International audience; The synthesis of a tridentate NNN ligand incorporating an amidoquinoline and an iminophosphorane (L R H, R =Ph, Cy) was carried out. Coordination to Pd II and Ni II precursors gave as expected square planar complexes of general formula [L R MCl]. The most surprising result came from the reaction of L Ph H with [Ni(COD)2] which gave a Ni II-phenyl complex bearing a tridentate amidoquinoline-aminophosphine ligand. This rearrangement would result from a proton transfer assisted by the Ni 0 when stabilized by a phenyl substituent at the phosphorus, as suggested by DFT calculations and complementary experiments. This nickel-phenyl complex formed the corresponding benzoyl complex under a CO atmosphere. more...
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- 2020
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14. Reductive Disproportionation of CO2 with Bulky Divalent Samarium Complexes
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Violaine Goudy, Augustin Braun, Grégory Nocton, Christos E. Kefalidis, Mathieu Xémard, Laurent Maron, Marie Cordier, Carine Clavaguéra, Elisa Louyriac, Louis Ricard, Maxime Tricoire, and Ludovic Castro more...
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chemistry.chemical_classification ,010405 organic chemistry ,Dimer ,Organic Chemistry ,Inorganic chemistry ,chemistry.chemical_element ,Disproportionation ,010402 general chemistry ,01 natural sciences ,Medicinal chemistry ,0104 chemical sciences ,3. Good health ,Divalent ,Adduct ,Inorganic Chemistry ,Samarium ,Solvent ,chemistry.chemical_compound ,chemistry ,Pyridine ,Physical and Theoretical Chemistry ,Diethyl ether - Abstract
The base-free divalent samarium complex Cptt2Sm (1; Cptt = 1,3-(tBu)2(C5H3)) has been synthesized in diethyl ether by salt metathesis of SmI2. Crystals of 1 suitable for X-ray study have been obtained by sublimation at 116 °C under reduced pressure. The dissolution of 1 in thf and pyridine solution leads to the solvent adducts Cptt2Sm(thf)2 (3) and Cptt2Sm(py) (4), respectively, while drying 3 under reduced pressure yields CpttSm(thf) (5). The reaction of CO2 with the base-free divalent samarium complexes Cptt2Sm (1) and Cpttt2Sm (2; Cpttt =1,2,4-(tBu)3(C5H2)) leads to the clean formation of bridged carbonate samarium dimers [Cpttt2Sm]2(μ-CO3) (7) and [Cptt2Sm]2(μ-CO3) (8). This is indicative of the reductive disproportionation of CO2 in both cases with release of CO. This contrasts with the formation of the oxalate-bridged samarium dimer reported from the reaction of CO2 with the Cp*2Sm(thf)2 complex. Otherwise, the reaction with CO does not proceed with the bulky complexes, while traces of O2 have led t... more...
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- 2017
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15. Redox activity of a dissymmetric ligand bridging divalent ytter-bium and reactive nickel fragments
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Jules Moutet, Ding Wang, Maxime Tricoire, Grégory Nocton, Valeriu Cemortan, Laboratoire de chimie moléculaire (LCM), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X) more...
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chemistry.chemical_classification ,Lanthanide ,010405 organic chemistry ,Ligand ,chemistry.chemical_element ,010402 general chemistry ,01 natural sciences ,Article ,0104 chemical sciences ,Divalent ,Inorganic Chemistry ,Nickel ,Crystallography ,chemistry.chemical_compound ,Electron transfer ,Deprotonation ,chemistry ,Moiety ,[CHIM]Chemical Sciences ,Homoleptic - Abstract
International audience; The reaction of a reactive nickel dimethyl 1 bearing a redox-active, dissymmetric ligand, which is obtained by deprotonation of 2-pyrimidin-2-yl-1H-benzimidazole (Hbimpm) with a divalent lanthanide complex, Cp* 2 Yb(OEt 2), affords an unprecedented, trimeric 2 with C(sp 3)-C(sp 3) bond formation between two ligands in an exo position. Meanwhile, the transient, dimeric species 3 can be isolated with the same ligand coupling fashion, however, with a drastic distorsion angle of the bimpm ligand and reactive NiMe 2 fragment, revealing the possible mechanism of this rearrangement. A much more stable dimeric congener, 5, with an exo ligand coupling, is synthesized in the presence of 18-crown-6, which captures the potassium counter ion. The CC coupling formation between two bimpm ligands results from the effective electron transfer from divalent lanthanide fragments. Without the divalent lanthanide, the reductive coupling occurs on a different carbon of the ligand, nicely showing the modulation of the spin density induced by the presence of the lanthanide ion. The electronic structures of these complexes are investigated by magnetic study (SQUID), indicating a 2 F 7/2 ground state for each ytterbium in all the heterometallics. This work firstly reports ligand coupling reactivity in a redox-active, yet dissymmetric system with divalent organolanthanides, and the reactive nickel moiety can impact the intriguing transition towards a stable homoleptic, trinulear lanthanide species. more...
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- 2020
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16. Cobalt-Catalyzed C(sp2)–CN Bond Activation: Cross-Electrophile Coupling for Biaryl Formation and Mechanistic Insight
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Jeanne-Marie Begouin, Corinne Gosmini, Vincent Gandon, Céline Dorval, Maxime Tricoire, Laboratoire de chimie moléculaire (LCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), and Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS) more...
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inorganic chemicals ,Aryl halide ,chemistry.chemical_element ,010402 general chemistry ,01 natural sciences ,Catalysis ,chemistry.chemical_compound ,biaryl ,reductive cross-coupling ,Reactivity (chemistry) ,cross-electrophile coupling ,Lewis acids and bases ,chemistry.chemical_classification ,catalysis ,010405 organic chemistry ,Chemistry ,Aryl ,benzonitriles ,General Chemistry ,[CHIM.CATA]Chemical Sciences/Catalysis ,Combinatorial chemistry ,cobalt ,0104 chemical sciences ,Benzonitrile ,Electrophile ,Cobalt - Abstract
International audience; Herein, we report a cross-electrophile coupling of benzonitrile derivatives and aryl halides with a simple cobalt-based catalytic system under mild conditions to form biaryl compounds. Even though the cobalt catalyst is able to activate the C(sp 2)−CN bond alone, the use of the AlMe 3 Lewis acid enhances the reactivity of benzonitriles and improves the cross-selectivity with barely any influence on the functional group compatibility. X-ray structure determination of an original low-valent cobalt species combined with catalytic and stoichiometric reactions reveals a catalytically active cobalt(I) species toward the aryl halide partner. On the other hand, experimental insights, including cyclic voltammetry experiments, suggest the involvement of a cobalt complex of a lower oxidation state to activate the benzonitrile derivative. Finally, density functional theory calculations support the proposed mechanistic cycle involving two low-valent cobalt species of different oxidation states to perform the reaction. more...
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- 2020
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17. Cover Feature: Size‐Controlled Hapticity Switching in [Ln(C 9 H 9 )(C 8 H 8 )] Sandwiches (Chem. Eur. J. 54/2021)
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Jeffrey D. Rinehart, Jeremy D. Hilgar, Olivier Cador, Mario Ruben, Frédéric Gendron, Jules Moutet, Nolwenn Mahieu, Luca Münzfeld, Peter W. Roesky, Grégory Nocton, Léo La Droitte, Boris Le Guennic, Eufemio Moreno-Pineda, and Maxime Tricoire more...
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Feature (computer vision) ,Chemical physics ,Chemistry ,Organic Chemistry ,Hapticity ,Cover (algebra) ,General Chemistry ,Catalysis - Published
- 2021
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18. Reversible electron transfer in organolanthanide chemistry
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Maxime Tricoire, Carine Clavaguéra, Arnaud Jaoul, Marie Cordier, Jules Moutet, Grégory Nocton, Laboratoire de chimie moléculaire (LCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), Laboratoire de Chimie-Physique (LCP), and Université de Cocody more...
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Lanthanide ,010405 organic chemistry ,Ligand ,Chemistry ,Crystal structure ,010402 general chemistry ,01 natural sciences ,Quantum chemistry ,Redox ,Article ,0104 chemical sciences ,[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry ,Electron transfer ,quantum chemistry ,Crystallography ,Organolanthanide chemistry ,[CHIM.COOR]Chemical Sciences/Coordination chemistry ,lanthanides ,electron density analysis ,Isostructural ,Palladium ,Platinum - Abstract
International audience; This article relates the synthesis and characterization of novel heterobimetallic complexes containing a low-valent lanthanide, a tetradentate redox non-innocent ligand, viz. the 4,5,9,10-tetraazaphenanthrene, taphen ligand and transition metal fragments of PdMe 2 and PtMe 2. The experimental results are supported by a theoretical study. Investigation of their reduction properties allowed the formation of isostructural original heterotrimetallic complexes containing two Cp* 2 Yb fragments and the (taphen)MMe 2 (M = Pd and Pt) motifs. These complexes are stable in non-coordinating solvent such as toluene but decompose in coordinating solvents such as thf. Investigation of the internal electron transfer shows that the taphen ligand behaves as a two-electrons reservoir but is capable of transferring back only one electron in thf. This reversible electron(s) transfer is rare in organolanthanide chemistry and show the potential interest of these complexes in reductive chemistry. Additionally, the trinuclear complexes feature odd X-ray crystal structures in which a deviation of symmetry is observed. The latter observation was studied in depth using quantum chemistry calculations highlighting the role of non-covalent weak interactions. more...
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- 2019
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19. Magnetism and variable temperature and pressure crystal structures of a linear oligonuclear cobalt bis-semiquinonate
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Marcel Diehl, Mette Andersen Borup, Louise H. Møller, James P. S. Walsh, Jacob Overgaard, Eva Rentschler, and Maxime Tricoire
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Phase transition ,Valence (chemistry) ,010405 organic chemistry ,Chemistry ,Crystal structure ,010402 general chemistry ,01 natural sciences ,Magnetic susceptibility ,0104 chemical sciences ,Inorganic Chemistry ,Crystallography ,Trigonal bipyramidal molecular geometry ,Electron transfer ,Molecular geometry ,Coordination geometry - Abstract
The crystal structure of the first oligomeric cobalt dioxolene complex, Co3(3,5-DBSQ)2((t)BuCOO)4(NEt3)2, 1, where DBSQ is 3,5-di-tert-butyl-semiquinonate, has been studied at various temperatures between 20 and 200 K. Despite cobalt-dioxolene complexes being generally known for their extensive ability to exhibit valence tautomerism (VT), we show here that the molecular geometry of compound 1 is essentially unchanged over the full temperature range, indicating the complete absence of electron transfer between ligand and metal. Magnetic susceptibility measurements clearly support the lack of VT between 8 and 300 K. The crystal structure is also determined at elevated pressures in the range from 0 to 2.5 GPa. The response of the crystal structure is surprisingly dependent on the dynamics of pressurisation: following rapid pressurization to 2 GPa, a structural phase transition occurs; yet, this is absent when the pressure is increased incrementally to 2.6 GPa. In the new high pressure phase, Z' is 2 and one of the two molecules displays changes in the coordination of one bridging carboxylate from μ2:κO:κO' to μ2:κ(2)O,O':κO', while the other molecule remains unchanged. Despite the significant changes to the molecular connectivity, analysis of the crystal structures shows that the phase transition leaves the spin and oxidation states of the molecules unaltered. Intermolecular interactions in the high pressure crystal structures have been analysed using Hirshfeld surfaces but they cannot explain the origin of the phase transition. The lack of VT in this first oligomeric Co-dioxolene complex is speculated to be due to the coordination geometry of the terminal Co-atoms, which are trigonal bipyramidally coordinated, different from the more common octahedral coordination. The energy that is gained by a hs-to-ls change in Oh is equal to Δ, while in the case of the trigonal bipyramidal (C3v), the energy gain is equal to the splitting between d(z(2)) and degenerate d(x(2) - y(2))/d(xy), which is significantly less. more...
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- 2016
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20. KevoreeJS: Enabling Dynamic Software Reconfigurations in the Browser
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Grégory Nain, Gerson Sunyé, Olivier Barais, Manuel Leduc, Johann Bourcier, Brice Morin, Francois Fouquet, Ludovic Mouline, Maxime Tricoire, Diversity-centric Software Engineering (DiverSe), Inria Rennes – Bretagne Atlantique, Institut National de Recherche en Informatique et en Automatique (Inria)-Institut National de Recherche en Informatique et en Automatique (Inria)-LANGAGE ET GÉNIE LOGICIEL (IRISA-D4), Institut de Recherche en Informatique et Systèmes Aléatoires (IRISA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Bretagne Sud (UBS)-École normale supérieure - Rennes (ENS Rennes)-Institut National de Recherche en Informatique et en Automatique (Inria)-Télécom Bretagne-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Bretagne Sud (UBS)-École normale supérieure - Rennes (ENS Rennes)-Institut National de Recherche en Informatique et en Automatique (Inria)-Télécom Bretagne-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche en Informatique et Systèmes Aléatoires (IRISA), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Bretagne Sud (UBS)-École normale supérieure - Rennes (ENS Rennes)-Télécom Bretagne-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), Security, Reliability and Trust Interdisciplibary Research Centre (S'nT), Université du Luxembourg (Uni.lu), Modeling Technologies for Software Production, Operation, and Evolution (AtlanModels), Laboratoire d'Informatique de Nantes Atlantique (LINA), Mines Nantes (Mines Nantes)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Mines Nantes (Mines Nantes)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Département informatique - EMN, Mines Nantes (Mines Nantes)-Inria Rennes – Bretagne Atlantique, Institut National de Recherche en Informatique et en Automatique (Inria)-Institut National de Recherche en Informatique et en Automatique (Inria), Stiftelsen for INdustriell og TEknisk Forskning Digital [Trondheim] (SINTEF Digital), ACM Sigsoft, European Project: 611337,EC:FP7:ICT,FP7-ICT-2013-10,HEADS(2013), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Bretagne Sud (UBS)-École normale supérieure - Rennes (ENS Rennes)-Institut National de Recherche en Informatique et en Automatique (Inria)-Télécom Bretagne-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes 1 (UR1), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Bretagne Sud (UBS)-École normale supérieure - Rennes (ENS Rennes)-Institut National de Recherche en Informatique et en Automatique (Inria)-Télécom Bretagne-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche en Informatique et Systèmes Aléatoires (IRISA), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Bretagne Sud (UBS)-École normale supérieure - Rennes (ENS Rennes)-Télécom Bretagne-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Mines Nantes (Mines Nantes)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Mines Nantes (Mines Nantes)-Université de Nantes (UN)-Département informatique - EMN, LANGAGE ET GÉNIE LOGICIEL (IRISA-D4), CentraleSupélec-Télécom Bretagne-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National de Recherche en Informatique et en Automatique (Inria)-École normale supérieure - Rennes (ENS Rennes)-Université de Bretagne Sud (UBS)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-CentraleSupélec-Télécom Bretagne-Université de Rennes 1 (UR1), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Institut de Recherche en Informatique et Systèmes Aléatoires (IRISA), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Inria Rennes – Bretagne Atlantique, and Institut National de Recherche en Informatique et en Automatique (Inria) more...
- Subjects
Computer science [C05] [Engineering, computing & technology] ,Resource-oriented architecture ,business.industry ,Computer science ,020207 software engineering ,02 engineering and technology ,[INFO.INFO-SE]Computer Science [cs]/Software Engineering [cs.SE] ,Sciences informatiques [C05] [Ingénierie, informatique & technologie] ,computer.software_genre ,Software framework ,Multilayered architecture ,020204 information systems ,Applications architecture ,0202 electrical engineering, electronic engineering, information engineering ,Operating system ,Reference architecture ,Software engineering ,business ,Software architecture ,Space-based architecture ,computer ,Software architecture description ,Dynamic component model ,Single page application ,Web Engineering - Abstract
International audience; The architecture of classic productivity software are moving from a traditional desktop-based software to a client server architecture hosted in the Cloud. In this context, web browsers behave as application containers that allow users to access a variety of Cloud-based applications and services, such as IDEs, Word processors, Music Collection Managers, etc. As a result, a significant part of these software run in the browser and accesses remote services. A lesson learned from development framework used in distributed applications is the success of pluggable architecture pattern as a core architecture concept, i.e., a Software Architecture that promotes the use of Pluggable Module to dynamically plug. Following this trend, this paper discusses the main challenges to create a component-based platform supporting the development of dynamically adaptable single web page applications. This paper also presents an approach called KevoreeJS based on models@runtime to control browser as component platform which address some of these challenges. We validate this work by presenting the design of a dashboard for sensor based system and highlighting the capacity of KevoreeJS to dynamically choose the placement of code on the server or client side and how KevoreeJS can be used to dynamically install or remove running components. more...
- Published
- 2016
- Full Text
- View/download PDF
21. Multitier diversification in Web-based software applications
- Author
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Johann Bourcier, Erwan Daubert, Benoit Baudry, Maxime Tricoire, Simon Allier, Olivier Barais, Martin Monperrus, Franck Fleurey, Hui Song, Diversity-centric Software Engineering (DiverSe), LANGAGE ET GÉNIE LOGICIEL (IRISA-D4), Institut de Recherche en Informatique et Systèmes Aléatoires (IRISA), CentraleSupélec-Télécom Bretagne-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National de Recherche en Informatique et en Automatique (Inria)-École normale supérieure - Rennes (ENS Rennes)-Université de Bretagne Sud (UBS)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-CentraleSupélec-Télécom Bretagne-Université de Rennes 1 (UR1), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Institut de Recherche en Informatique et Systèmes Aléatoires (IRISA), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Inria Rennes – Bretagne Atlantique, Institut National de Recherche en Informatique et en Automatique (Inria), Stiftelsen for INdustriell og TEknisk Forskning Digital [Trondheim] (SINTEF Digital), Self-adaptation for distributed services and large software systems (SPIRALS), Inria Lille - Nord Europe, Institut National de Recherche en Informatique et en Automatique (Inria)-Institut National de Recherche en Informatique et en Automatique (Inria)-Centre de Recherche en Informatique, Signal et Automatique de Lille - UMR 9189 (CRIStAL), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université de Lille, Sciences et Technologies, Théorie économique, modélisation et applications (THEMA), Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine-Centre National de la Recherche Scientifique (CNRS), European Project: 600654,EC:FP7:ICT,FP7-ICT-2011-9,DIVERSIFY(2013), Inria Rennes – Bretagne Atlantique, Institut National de Recherche en Informatique et en Automatique (Inria)-Institut National de Recherche en Informatique et en Automatique (Inria)-LANGAGE ET GÉNIE LOGICIEL (IRISA-D4), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Bretagne Sud (UBS)-École normale supérieure - Rennes (ENS Rennes)-Institut National de Recherche en Informatique et en Automatique (Inria)-Télécom Bretagne-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS)-Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Bretagne Sud (UBS)-École normale supérieure - Rennes (ENS Rennes)-Institut National de Recherche en Informatique et en Automatique (Inria)-Télécom Bretagne-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche en Informatique et Systèmes Aléatoires (IRISA), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Bretagne Sud (UBS)-École normale supérieure - Rennes (ENS Rennes)-Télécom Bretagne-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS) more...
- Subjects
Social software engineering ,Engineering ,business.industry ,Software development ,[INFO.INFO-SE]Computer Science [cs]/Software Engineering [cs.SE] ,computer.software_genre ,Software framework ,Component-based software engineering ,Software construction ,Systems engineering ,Package development process ,Dependability ,business ,Software engineering ,Web application development ,computer ,Software - Abstract
International audience; Internet applications are formed from reusable components all over the software stack. Both on the client and the server side, web-specific libraries and frameworks enable creative developers to wrap up rich applications within very short time. Reuse and modularity are key for liberating creativity and entrepreneurship in the Internet world. However, this bright world has a darker side. The problem is that they participate in creating a massive monoculture, in a way that has never been encountered before. We propose to counter this phenomenon by extending software diversification beyond the operating system level. The way to go is to diversify the different layers, up to the functional code. We have experimented with a realistic Internet application to demonstrate the feasibility of multi-tier diversification. This experiment highlights the challenges that are ahead of software engineers if they want to systematically break the applicative monoculture of Internet applications. more...
- Published
- 2015
- Full Text
- View/download PDF
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