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1. Combining electron transfer, spin crossover, and redox properties in metal-organic frameworks

Author

Livia Getzner, Damian Paliwoda, Laure Vendier, Latévi Max Lawson-Daku, Aurelian Rotaru, Gábor Molnár, Saioa Cobo, and Azzedine Bousseksou

Subjects
Science
Abstract

Abstract Hofmann coordination polymers (CPs) that couple the well-studied spin transition of the FeII central ion with electron-responsive ligands provide an innovative strategy toward multifunctional metal-organic frameworks (MOFs). Here, we developed a 2D planar network consisting of metal-cyanide-metal sheets in an unusual coordination mode, brought about by infinitely π-stacked redox-active bipyridinium derivatives as axial ligands. The obtained family of materials show vivid thermochromism attributed to electron transfer and/or electronic spin state change processes that can occur either independently or concomitantly. Importantly, the redox activity of the ligands within the structure leads to the quasi-reversible electrochemical reduction reaction on a spin-crossover complex at solid state. These observations have been confirmed via temperature-dependent single-crystal X-ray diffraction, magnetic measurements, Mössbauer, EPR, optical and vibrational spectroscopies as well as quantum chemical calculations.

Published
2024
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3. Mechanochemical Studies on Coupling of Hydrazines and Hydrazine Amides with Phenolic and Furanyl Aldehydes—Hydrazones with Antileishmanial and Antibacterial Activities

Author

Anna Kapusterynska, Christian Bijani, Damian Paliwoda, Laure Vendier, Valérie Bourdon, Nicolas Imbert, Sandrine Cojean, Philippe Marie Loiseau, Deborah Recchia, Viola Camilla Scoffone, Giulia Degiacomi, Abdul Akhir, Deepanshi Saxena, Sidharth Chopra, Vira Lubenets, and Michel Baltas

Subjects
mechanochemistry, sustainable synthesis, hydrazones, furanyls, phenolics, anti-infectious, Organic chemistry, QD241-441
Abstract

Hydrazone compounds represent an important area of research that includes, among others, synthetic approaches and biological studies. A series of 17 hydrazones have been synthesized by mechanochemical means. The fragments chosen were phenolic and furanyl aldehydes coupled with 12 heterocyclic hydrazines or hydrazinamides. All compounds can be obtained quantitatively when operating on a planetary ball mill and a maximum reaction time of 180 min (6 cycles of 30 min each). Complete spectroscopic analyses of hydrazones revealed eight compounds (3–5, 8–11, 16) present in one geometric form, six compounds (1, 2, 13–15) present in two isomeric forms, and three compounds (6, 7, 12) where one rotation is restricted giving rise to two different forms. The single crystal X-ray structure of one of the hydrazones bearing the isoniazid fragment (8) indicates a crystal lattice consisting of two symmetry-independent molecules with different geometries. All compounds obtained were tested for anti-infectious and antibacterial activities. Four compounds (1, 3, 5 and 8) showed good activity against Mycobacterium tuberculosis, and one (7) was very potent against Staphylococcus aureus. Most interesting, this series of compounds displayed very promising antileishmanial activity. Among all, compound 9 exhibited an IC50 value of 0.3 µM on the Leishmania donovani intramacrophage amastigote in vitro model and a good selectivity index, better than miltefosine, making it worth evaluating in vivo.

Published
2023
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4. Redox-Switchable Behavior of Transition-Metal Complexes Supported by Amino-Decorated N-Heterocyclic Carbenes

Author

Mirko Ruamps, Stéphanie Bastin, Lionel Rechignat, Alix Sournia-Saquet, Laure Vendier, Noël Lugan, Jean-Marie Mouesca, Dmitry A. Valyaev, Vincent Maurel, and Vincent César

Subjects
redox-active ligands, N-heterocyclic carbene, organometallic complexes, EPR spectroscopy, DFT calculations, Organic chemistry, QD241-441
Abstract

The coordination chemistry of the N-heterocyclic carbene ligand IMes(NMe2)2, derived from the well-known IMes ligand by substitution of the carbenic heterocycle with two dimethylamino groups, was investigated with d6 [Mn(I), Fe(II)], d8 [Rh(I)], and d10 [Cu(I)] transition-metal centers. The redox behavior of the resulting organometallic complexes was studied through a combined experimental/theoretical study, involving electrochemistry, EPR spectroscopy, and DFT calculations. While the complexes [CuCl(IMes(NMe2)2)], [RhCl(COD)(IMes(NMe2)2)], and [FeCp(CO)2 (IMes(NMe2)2)](BF4) exhibit two oxidation waves, the first oxidation wave is fully reversible but only for the first complex the second oxidation wave is reversible. The mono-oxidation event for these complexes occurs on the NHC ligand, with a spin density mainly located on the diaminoethylene NHC-backbone, and has a dramatic effect on the donating properties of the NHC ligand. Conversely, as the Mn(I) center in the complex [MnCp(CO)2 ((IMes(NMe2)2)] is easily oxidizable, the latter complex is first oxidized on the metal center to form the corresponding cationic Mn(II) complex, and the NHC ligand is oxidized in a second reversible oxidation wave.

Published
2022
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5. Chlorido(η6-N2-diphenylphosphanyl-N1,N1-diisopropyl-4-methoxybenzamidine-κP)(triphenylphosphane-κP)ruthenium(II) trifluoromethansulfonate acetone disolvate

Author

Alain Igau, Laure Vendier, and Manel Kéchaou-Perrot

Subjects
Crystallography, QD901-999
Abstract

In the title compound, [RuCl(C18H15P)(C26H31N2OP)](CF3O3S)·2C3H6O, the RuII ion is coordinated in a three-legged piano stool, half-sandwich-type geometry by a chlorido ligand, a triphenylphosphine and a tethered η6-(phenyl-p-O-methoxy) κ1-P N-diphenylphosphino N′-diisopropyl amidine ligand charge-balanced by a trifluormethansulfonate counter-anion. The η6-coordination mode of the arene incorporated into the structure was generated in situ after addition of methyl trifluoromethanesulfonate to the neutral η5-arene tethered precursor complex [RuCl(PPh3)(η5:κ1-OC6H4C(NiPr2)=N-PPh2)] in dichloromethane solution.

Published
2013
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6. Bis(2,2′-bipyridine)[1,9-bis(diphenylphosphanyl)-1,2,3,4,6,7,8,9-octahydropyrimido[1,2-a]pyrimidin-5-ium]ruthenium(II) hexafluoridophosphate dibromide dichloromethane disolvate monohydrate

Author

Alain Igau, Pierre Sutra, Laure Vendier, and Congcong Shang

Subjects
Crystallography, QD901-999
Abstract

In the cation of the title complex, [Ru(C31H32N3P2)(C10H8N2)2](PF6)(Br)2·2CH2Cl2·H2O, the ruthenium ion is coordinated in a distorted octahedral geometry by two 2,2′-bipyridine (bpy) ligands and a chelating cationic N-diphenylphosphino-1,3,4,6,7,8-hexahydro-2-pyrimido[1,2-a]pyrimidine [(PPh2)2-hpp] ligand. The tricationic charge of the complex is balanced by two bromide and one hexafluoridophosphate counter-anions. The compound crystallized with two molecules of dichloromethane (one of which is equally disordered about a Cl atom) and a water molecule. In the crystal, one of the Br anions bridges two water molecules via O—H...Br hydrogen bonds, forming a centrosymmetric diamond-shaped R42(8) motif. The cation and anions and the solvent molecules are linked via C—H...F, C—H...Br, C—H...Cl and C—H...O hydrogen bonds, forming a three-dimensional network.

Published
2013
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7. 3-Methyl-1-propargylquinoxalin-2(1H)-one

Author

Hanane Benzeid, Youssef Ramli, Laure Vendier, El Mokhtar Essassi, and Seik Weng Ng

Subjects
Crystallography, QD901-999
Abstract

The ten-membered fused ring of the title compound, C12H10N2O, is essentially planar in the two independent molecules of the asymmetric unit (r.m.s. deviations = 0.012 and 0.015 Å).

Published
2009
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8. 1-Ethyl-3-methylquinoxalin-2(1H)-one

Author

Hanane Benzeid, Laure Vendier, Youssef Ramli, Bernard Garrigues, and El Mokhtar Essassi

Subjects
Crystallography, QD901-999
Abstract

The asymmetric unit of the title compound, C11H12N2O, contains two independent molecules. In the crystal structure, intermolecular C—H...O hydrogen bonds link the molecules. There are π–π contacts between the quinoxaline rings [centroid–centroid distances = 3.446 (2), 3.665 (2), 3.645 (3) and 3.815 (3) Å]. There also exist C—H...π contacts between the methyl groups and the quinoxaline rings.

Published
2008
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10. Design of Anti-infectious Agents from Lawsone in a Three-Component Reaction with Aldehydes and Isocyanides

Author

Christina L. Koumpoura, Michel Nguyen, Christian Bijani, Laure Vendier, Elena G. Salina, Silvia Buroni, Giulia Degiacomi, Sandrine Cojean, Philippe M. Loiseau, Françoise Benoit-Vical, Alfonso T. García-Sosa, null Anne Robert, Michel Baltas, Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT-FR 2599), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), New Antimalarial Molecules and Pharmacological Approaches (ERL1289), Centre d'investigation clinique de Toulouse (CIC 1436), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Pôle Santé publique et médecine publique [CHU Toulouse], Centre Hospitalier Universitaire de Toulouse (CHU Toulouse)-Centre Hospitalier Universitaire de Toulouse (CHU Toulouse)-Université Toulouse III - Paul Sabatier (UT3), Centre Hospitalier Universitaire de Toulouse (CHU Toulouse)-Centre Hospitalier Universitaire de Toulouse (CHU Toulouse), Russian Academy of Sciences [Moscow] (RAS), Dipartimento di Biologia e Biotecnologie 'Lazzaro Spallanzani' = Department of Biology and Biotechnology [Univ di Pavia] (DBB UNIPV), Università degli Studi di Pavia = University of Pavia (UNIPV), Biomolécules : Conception, Isolement, Synthèse (BioCIS), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-CY Cergy Paris Université (CY), University of Tartu, Centre National de la Recherche Scientifique (CNRS), Université Paul Sabatier, Institut National de la Santé et de la Recherche Médicale (INSERM), Fondation pour la Recherche Médicale (FRM), Paris Saclay University, Estonian Research Council, Italian Ministry of Education, University and Research (MIUR), University of Pavia, Gulli, Marie-Hélène, Institut de Chimie de Toulouse (ICT), 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)-Centre National de la Recherche Scientifique (CNRS), and Université de Toulouse (UT)-Université de Toulouse (UT)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Pôle Santé publique et médecine publique [CHU Toulouse]

Subjects
Aldehydes, Inorganic carbon compounds, General Chemical Engineering, Multicomponent reactions, [SDV.BBM] Life Sciences [q-bio]/Biochemistry, Molecular Biology, Reaction products, [SDV.BBM]Life Sciences [q-bio]/Biochemistry, Molecular Biology, General Chemistry, Carbon
Abstract

International audience; The first effective synthetic approach to naphthofuroquinones via a reaction involving lawsone, various aldehydes, and three isocyanides under microwave irradiation afforded derivatives in moderate to good yields. In addition, for less-reactive aldehydes, two naphtho-enaminodione quinones were obtained for the first time, as result of condensation between lawsone and isocyanides. X-ray structure determination for 9 and 2D-NMR spectra of 28 confirmed the obtained structures. All compounds were evaluated for their anti-infectious activities against Plasmodium falciparum, Leishmania donovani, and Mycobacterium tuberculosis. Among the naphthofuroquinone series, 17 exhibited comparatively the best activity against P. falciparum (IC50 = 2.5 μM) and M. tuberculosis (MIC = 9 μM) with better (P. falciparum) or equivalent (M. tuberculosis) values to already-known naphthofuroquinone compounds. Among the two naphtho-enaminodione quinones, 28 exhibited a moderate activity against P. falciparum with a good selectivity index (SI > 36) while also a very high potency against L. donovani (IC50 = 3.5 μM and SI > 28), rendering it very competitive to the reference drug miltefosine. All compounds were studied through molecular modeling on their potential targets for P. falciparum, Pfbc1, and PfDHODH, where 17 showed the most favorable interactions.

Published
2022
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11. Mechanochemical Studies on Coupling of Hydrazines and Hydrazine Amides with Phenolic and Furanyl Aldehydes—Hydrazones with Antileishmanial and Antibacterial Activities

Author

Baltas, Anna Kapusterynska, Christian Bijani, Damian Paliwoda, Laure Vendier, Valérie Bourdon, Nicolas Imbert, Sandrine Cojean, Philippe Marie Loiseau, Deborah Recchia, Viola Camilla Scoffone, Giulia Degiacomi, Abdul Akhir, Deepanshi Saxena, Sidharth Chopra, Vira Lubenets, and Michel

Subjects
mechanochemistry, sustainable synthesis, hydrazones, furanyls, phenolics, anti-infectious, antileishmanial, antibacterial
Abstract

Hydrazone compounds represent an important area of research that includes, among others, synthetic approaches and biological studies. A series of 17 hydrazones have been synthesized by mechanochemical means. The fragments chosen were phenolic and furanyl aldehydes coupled with 12 heterocyclic hydrazines or hydrazinamides. All compounds can be obtained quantitatively when operating on a planetary ball mill and a maximum reaction time of 180 min (6 cycles of 30 min each). Complete spectroscopic analyses of hydrazones revealed eight compounds (3–5, 8–11, 16) present in one geometric form, six compounds (1, 2, 13–15) present in two isomeric forms, and three compounds (6, 7, 12) where one rotation is restricted giving rise to two different forms. The single crystal X-ray structure of one of the hydrazones bearing the isoniazid fragment (8) indicates a crystal lattice consisting of two symmetry-independent molecules with different geometries. All compounds obtained were tested for anti-infectious and antibacterial activities. Four compounds (1, 3, 5 and 8) showed good activity against Mycobacterium tuberculosis, and one (7) was very potent against Staphylococcus aureus. Most interesting, this series of compounds displayed very promising antileishmanial activity. Among all, compound 9 exhibited an IC50 value of 0.3 µM on the Leishmania donovani intramacrophage amastigote in vitro model and a good selectivity index, better than miltefosine, making it worth evaluating in vivo.

Published
2023
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15. Syntheses of N2-bridged heterobimetallic complexes, their structural and qualitative bonding analyses

Author

Quentin Le Dé, Fourat Orbay, Laure Vendier, Antoine Simonneau, Laboratoire de chimie de coordination (LCC), 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)-Centre National de la Recherche Scientifique (CNRS), European Research Council (ERC) (Grant Agreement 757501 - OrFuNCo (Organic Functionalisation of N2 Using Metal-Main Group and Metal-Metal Cooperativity)) 2018-2023, and CNRS

Subjects
Inorganic Chemistry, Molybdenum, Dinitrogen, Organic Chemistry, Molecular orbitals, Materials Chemistry, Heterobimetallic complexes, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Biochemistry
Abstract

International audience; A series of N2-bridged (μ-η1:η1-N2) heterobimetallic complexes were prepared by the reaction of the dinitrogen complex [Mo(depe)2(N2)2] (depe = 1,2-bis(diethylphosphino)ethane) with the group IV-VI high valent metal halides [Cp2ZrCl2], NbCl5, TaCl5, MoCl5 and WCl4 via chloride substitution. Compounds [MoCl(depe)2(μ-N2)ZrCp2Cl] (1) and [MoCl(depe)2(μ-N2)M'Cl4(THF)] (2–5, M’ = Nb, Ta, Mo or W) were crystallized from the reaction mixtures. In the case of the reaction with WCl4, disproportionation of W(IV) was suspected but not evidenced. Single crystal X-ray diffraction analyses on all compounds allowed a systematic structural study, and the sketching of qualitative molecular orbital diagrams helped discussing the bonding situation and bolster the structural data.

Published
2023
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16. Towards ( C,C )‐cyclometalated N ‐(9‐alkylfluorenyl)NHC Ruthenium Complexes for Z ‐selective Olefin Metathesis

Author

Katarzyna Gajda, Adrian Sytniczuk, Laure Vendier, Bartosz Trzaskowski, Noël Lugan, Anna Kajetanowicz, Stéphanie Bastin, Karol Grela, Vincent César, Laboratoire de chimie de coordination (LCC), 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)-Centre National de la Recherche Scientifique (CNRS), Faculty of Chemistry, Warsaw University of Technology, Warsaw University of Technology [Warsaw], and Centre National de la Recherche Scientifique

Subjects
Inorganic Chemistry, Olefin metathesis, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, N-heterocyclic carbenes, [CHIM.CATA]Chemical Sciences/Catalysis, Migration, Ruthenium, Cyclometalation
Abstract

International audience; Three Hoveyda-Grubbs complexes supported by N-(9-alkylfluorenyl)imidazol-2-ylidene ligands (alkyl=methyl, ethyl or benzyl) have been synthesized. With the aim to generate chelating, cyclometalated (C,CNHC) ruthenium complexes for Z-selective olefin metathesis, the C(sp3)-H activation of the dangling alkyl group has been studied. While the methyl derivative leads to the expected cyclometalated complex, a C(sp2)-H activation of the fluorenyl moiety and no evolution/transformation are observed for the ethyl and benzyl derivatives, respectively. Although highly fragile under catalytic conditions, the cyclometalated complex leads to Z/E stereoselectivity up to 94/6. An unprecedented insertion of the alkylidene moiety into the Ru-CNHC bond leading to ruthenium N-heterocyclic olefin complexes is also observed and supported by calculations of the corresponding reaction pathway.

Published
2023
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17. Pressure Tuning of Coupled Structural and Spin State Transitions in the Molecular Complex [Fe(H

Author

Damian, Paliwoda, Laure, Vendier, William, Nicolazzi, Gábor, Molnár, and Azzedine, Bousseksou

Abstract

The large volume change, which accompanies the molecular spin crossover (SCO) phenomenon in some transition metal complexes, prompts frequently the coupling of the SCO with other instabilities. Understanding the driving mechanism(s) of such coupled phase transitions is not only important for fundamental reasons but also provides scope for the development of multifunctional materials. The general theoretical expectation is that the coupling has elastic origin, and the sequence of transitions can be tuned by an externally applied pressure, but dedicated experiments remain scarce. Here, we used high-pressure and low-temperature single-crystal X-ray diffraction to investigate the high-spin (HS) to low-spin (LS) transitions in the molecular complexes [Fe

Published
2022

19. X-Ray diffraction structure of Cu(II) and Zn(II) complexes of 8-aminoquinoline derivatives (TDMQ), related to the activity of these chelators as potential drugs against Alzheimer's disease

Author

Youzhi Li, Michel Nguyen, Laure Vendier, Anne Robert, Yan Liu, Bernard Meunier, School of Chemical Engineering and Light Industry, Guangdong University of Technology, Laboratoire de chimie de coordination (LCC), 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)-Centre National de la Recherche Scientifique (CNRS), New Antimalarial Molecules and Pharmacological Approaches (ERL1289), Centre d'investigation clinique de Toulouse (CIC 1436), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Pôle Santé publique et médecine publique [CHU Toulouse], Centre Hospitalier Universitaire de Toulouse (CHU Toulouse)-Centre Hospitalier Universitaire de Toulouse (CHU Toulouse)-Université Toulouse III - Paul Sabatier (UT3), Centre Hospitalier Universitaire de Toulouse (CHU Toulouse)-Centre Hospitalier Universitaire de Toulouse (CHU Toulouse), NSFC (grant 21502023), Guangdong Province (Program for Innovative Research Teams and Leading Talents Introduction, grant 2050205), GDUT (grant 220418037), CNRS, Gulli, Marie-Hélène, Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National de la Santé et de la Recherche Médicale (INSERM)-Pôle Santé publique et médecine publique [CHU Toulouse], Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-CHU Toulouse [Toulouse]-Institut National de la Santé et de la Recherche Médicale (INSERM)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-CHU Toulouse [Toulouse]-Institut National de la Santé et de la Recherche Médicale (INSERM)

Subjects
010405 organic chemistry, Copper chelator, Organic Chemistry, [CHIM.COOR] Chemical Sciences/Coordination chemistry, Alzheimer's disease, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, 3. Good health, Analytical Chemistry, Inorganic Chemistry, Zinc, 8-aminoquinoline, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Spectroscopy, X-ray crystallography
Abstract

International audience; TDMQ chelators have been designed as drug-candidates for the regulation of copper homeostasis and for the reduction of the oxidative stress in the brain of Alzheimer's patients. To achieve suitable biological properties and high Cu(II) selectivity in a zinc-rich medium, TDMQ ligands must meet critical coordination chemistry requirements related to the structures of the CuII-TDMQ complexes. The correlation between X-ray diffraction structures of Cu- and Zn-TDMQ complexes and their physicochemical properties should therefore help to draw pertinent correlations between structure and properties of the drug-candidates, and to select the most promising ones for biological studies. Here we report the X-ray structures of single crystals of Cu-TDMQ36, and of the zinc complexes of TDMQ35, TDMQ36 and TDMQ22. Comparison with the already reported structures of other copper and zinc complexes of TDMQ then allows to specify the structure requirement for potentially more efficient drugs.

Published
2022
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20. A Masked Form of an O‐Borylated Breslow Intermediate for the Diastereoselective FLP‐Type Activation of Aldehydes

Author

Angelica Mejia Fajardo, Nicolas Queyriaux, Aurèle Camy, Laure Vendier, Mary Grellier, Iker del Rosal, Laurent Maron, Sébastien Bontemps, Laboratoire de chimie de coordination (LCC), 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)-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), 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), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), CNRS, and ANR-17-CE07-0015,ICC,Cycle de Calvin Inorganic(2017)

Subjects
FLP activation, Diastereoselective activation, Organic Chemistry, Breslow intermediates, CO2, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Chemistry, Boranes, Catalysis
Abstract

International audience; Breslow intermediates are very often elusive species whose application in frustrated Lewis pair (FLP) chemistry is unprecedented. Described herein is the use of a masked form of an O-borylated Breslow (OBB) intermediate that performs FLP-type activation of the carbonyl function of five different benzaldehyde derivatives with complete diastereoselectivity. The resulting compounds are characterised in solution by NMR spectroscopy (compounds 4–8) and in solid state by X-ray diffraction analysis (compounds 4–6). A combined kinetic and theoretical investigation reveals the associative nature of the rate determining step and suggests that the OBB intermediate part is never released during the whole process.

Published
2022
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21. Helical chiral N‐heterocyclic carbene ligands in enantioselective gold catalysis

Author

Lenka Pallova, Laura Abella, Marion Jean, Nicolas Vanthuyne, Cécile Barthes, Laure Vendier, Jochen Autschbach, Jeanne Crassous, Stéphanie Bastin, Vincent César, Laboratoire de chimie de coordination (LCC), 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)-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry [Buffalo], University at Buffalo [SUNY] (SUNY Buffalo), State University of New York (SUNY)-State University of New York (SUNY), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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), Institut de Physique de Rennes (IPR), Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS), National Science Foundation (Grant CHE-1855470), and ANR-16-CE07-0019,HEL-NHC,Carbènes N-hétérocycliques (NHC) hélicéniques: synthèse, structure, propriétés photophysiques et activité catalytique(2016)

Subjects
Organic Chemistry, Asymmetric catalysis, N-heterocyclic, Carbenes, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Chemistry, Gold, Chirality, Catalysis, Helicenes
Abstract

International audience; The first chiral helicene-NHC gold(I) complexes efficient in enantioselective catalysis were prepared. The L-shaped chiral ligand is composed of an imidazo[1,5-a]pyridin-3-ylidene (IPy) scaffold laterally-substituted by a configurationally stable [5]-helicenoid unit. The chiral information was introduced in a key post-functionalization step of a NHC-gold(I) complex bearing a symmetrical anionic fluoreno[5]helicene substituent, leading to a racemic mixture of complexes featuring three correlated elements of chirality, namely central, axial and helical chirality. After HPLC enantiomeric resolution, X-ray crystallography and theoretical calculations enabled structural and stereochemical characterization of these configurationally stable NHC-gold(I) complexes. The high potential in asymmetric catalysis is demonstrated in the benchmark cycloisomerization of N-tethered 1,6-enynes with up to 95:5 er.

Published
2022
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22. Dinitrogen-derived (diarylboryl)diazenido Complexes with Differing Coordination to the Thallium Cation

Author

Amal Bouammali, Anaïs Coffinet, Laure Vendier, Antoine Simonneau, Laboratoire de chimie de coordination (LCC), 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)-Centre National de la Recherche Scientifique (CNRS), European Research Council (ERC) (Grant Agreement 757501), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Inorganic Chemistry, 010405 organic chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, 010402 general chemistry, equipment and supplies, 01 natural sciences, 3. Good health, 0104 chemical sciences
Abstract

International audience; To prepare N2-derived cationic boryldiazenido-tungsten complexes as models of semimetallic metal-borinium frustrated Lewis pairs activating N2, we have attempted halide abstraction from trans-(diarylboryl)diazenido-halo-tungsten complexes. Reactions with Tl+ led to adducts in which coordination of the cation differs depending on the boryldiazenide substituents and the ancillary ligand. Chloride scavenging was not observed.

Published
2022
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23. Shvo-Type Metal-Ligand Cooperative Catalysts: Tethered eta(5)-Oxocyclohexadienyl Ruthenium Complexes

Author

Emmanuel Puig, Raphaël Verron, Manel Kechaou-Perrot, Laure Vendier, Heinz Gornitzka, Karinne Miqueu, Jean-Marc Sotiropoulos, Cédric Fischmeister, Pierre Sutra, Alain Igau, Laboratoire de chimie de coordination (LCC), 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)-Centre National de la Recherche Scientifique (CNRS), 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), Centre scientifique et Technique Jean Feger (CSTJF), TOTAL FINA ELF, Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), MESR, ANR, Project CatEngy [ANR-18-CE07-0006-01], and ANR-18-CE07-0006,CatEngy,Catalyseurs avec Coopérativité Métal-Ligand pour une Energie Durable(2018)

Subjects
Inorganic Chemistry, Aromatic compounds, Catalysts, Transfer reactions, Metals, Organic Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Ligands
Abstract

International audience; Diverse synthetic routes of tethered eta(5)-oxocyclo-hexadienyl ruthenium complexes, which are the extended version of the eta(4)-cyclopentadienone Shvo-type active catalyst, are described and their reactivity studies are reported. An original dimeric eta(5)-oxocyclohexadienyl compound has been isolated and its solid-state structure was established by X-ray analysis. DFT computational data suggested that this dimeric compound is prone to generate a coordinatively unsaturated mononuclear Lewis acid metal complex bearing a Lewis basic pi-coordinated eta(5)-oxocyclohexadienyl Iigand. Preliminary studies in (transfer)-hydrogenation of acetophenone confirmed that the dimeric eta(5)-oxocyclohexadienyl complex behaves as a bifunctional catalyst with metal-ligand cooperativity. Promising results were obtained under base-free conditions using dihydrogen, iPrOH, and formic acid as hydrogen highlighting the robustness and stability of the catalyst and opening perspectives donors, the latter being active in water, hence toward sustainable catalytic transformations.

Published
2022
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24. NaLa(SO4)2,H2O thermal conversion and Na3La(SO4)3 crystal growth

Author

Hanae Azeroual, Laure Vendier, Amine Geneste, Dominique Granier, Laurent Alvarez, Patrick Hermet, Olivier Cambon, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Laboratoire de chimie de coordination (LCC), 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)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Charles Coulomb (L2C), and Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)

Subjects
single crystal x-ray diffraction, Lanthanum-based polyhedron, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Condensed Matter Physics, Electronic, Optical and Magnetic Materials, Inorganic Chemistry, Raman spectroscopy, H-bonds, [CHIM.CRIS]Chemical Sciences/Cristallography, Materials Chemistry, Ceramics and Composites, Physical and Theoretical Chemistry, Sodium Lanthanum sulfate, thermal decomposition
Abstract

International audience; NaLa(SO4)2,H2O crystalline powder was obtained under hydrothermal conditions at 220°C. A coupled TGA/DTA experiment of NaLa(SO4)2,H2O exhibits a weight loss at 260°C corresponding to the dehydration and an endothermal peak at 774°C. To elucidate the transformation mechanism as a function of temperature, single crystals have been grown at 80°C, 300 and 800°C. For each phase, single crystals have been isolated and structure determination was performed. As already published, NaLa(SO4)2,H2O crystallizes in a P3121 space group. However, the dehydration at 260°C is not a simple loss of the water molecule but a radical change in the structure. The removal of the water molecules inside the tunnels formed by the framework leads to a change in the coordination of the LaO9 Lanthanum-based polyhedrons. The compound obtained after dehydration is a new triple sulfate of the formula Na3La(SO4)3 crystallizing in the R-3 space group (a = 14.0976(1) Å; c = 8.1267(1) Å) with LaO12 icosahedrons. Millimeter size single crystals of this new phase have been grown under hydrothermal conditions (300°C, 157 bars). After the endothermal peak at 774°C, Na3La(SO4)3 decomposes by forming the anhydrous double sulfate NaLa(SO4)2 crystallizing in the P-1 space group with LaO10 polyhedrons. The structure of the three (NaLa)-compounds at RT, 300°C and 800°C is compatible with the expected Raman signatures. Finally, a complete transformation of NaLa(SO4)2,H2O up to 800°C is proposed. After 1000°C, the compound decomposes chemically with a large weight loss.

Published
2023
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25. Enantioselective Reductive Oligomerization of Carbon Dioxide into l-Erythrulose via a Chemoenzymatic Catalysis

Author

Sarah Desmons, Pere Clapés, Laure Vendier, Katie Grayson-Steel, Nelson Nuñez-Dallos, Sébastien Bontemps, Régis Fauré, Claire Dumon, John Hurtado, Ministerio de Ciencia e Innovación (España), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Toulouse Biotechnology Institute (TBI), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Universidad de los Andes [Bogota] (UNIANDES), Departamento de Química Biológica y Modelización Molecular, Instituto de Química Avanzada de Cataluña IQAC-CSIC, Barcelona, Région Midi-Pyrénées, Ministerio de Ciencia e Innovación (MICIN), Fondo Europeo de Desarrollo Regional (FEDER) (grant RTI2018-094637-B-I00), Programación Conjunta Internacional (PCI2018-092937) : initiative ERA CoBioTech (Tralaminol), ANR-17-CE07-0015,ICC,Cycle de Calvin Inorganic(2017), 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)-Centre National de la Recherche Scientifique (CNRS), and Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)

Subjects
Carbohydrates, Dihydroxyacetone, Context (language use), Peptides and proteins, 010402 general chemistry, 01 natural sciences, Biochemistry, Catalysis, chemistry.chemical_compound, Aldol reactions, Colloid and Surface Chemistry, Cascade reaction, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Redox reactions, Aldehydes, 010405 organic chemistry, Acetal, Enantioselective synthesis, General Chemistry, Carbon Dioxide, Combinatorial chemistry, 0104 chemical sciences, De novo synthesis, Hydroboration, chemistry
Abstract

A cell-free enantioselective transformation of the carbon atom of CO2 has never been reported. In the urgent context of transforming CO2 into products of high value, the enantiocontrolled synthesis of chiral compounds from CO2 would be highly desirable. Using an original hybrid chemoenzymatic catalytic process, we report herein the reductive oligomerization of CO2 into C3 (dihydroxyacetone, DHA) and C4 (l-erythrulose) carbohydrates, with perfect enantioselectivity of the latter chiral product. This was achieved with the key intermediacy of formaldehyde. CO2 is first reduced selectively by 4e– by an iron-catalyzed hydroboration reaction, leading to the isolation and complete characterization of a new bis(boryl)acetal compound derived from dimesitylborane. In an aqueous buffer solution at 30 °C, this compound readily releases formaldehyde, which is then involved in selective enzymatic transformations, giving rise either (i) to DHA using a formolase (FLS) catalysis or (ii) to l-erythrulose with a cascade reaction combining FLS and d-fructose-6-phosphate aldolase (FSA) A129S variant. Finally, the nature of the synthesized products is noteworthy, since carbohydrates are of high interest for the chemical and pharmaceutical industries. The present results prove that the cell-free de novo synthesis of carbohydrates from CO2 as a sustainable carbon source is a possible alternative pathway in addition to the intensely studied biomass extraction and de novo syntheses from fossil resources., We wish to thank the reviewers, whose comments helped to improve the manuscript and in particular the 1H NMR interpretation of compound 3-13C. S.D. thanks Région Midi-Pyrénées and Université Fédérale de Toulouse for a doctoral fellowship. S.B. thanks the ANR programme JCJC “ICC”. C. Bijani is gratefully acknowledged for his help in the simulation of 3-13C. K.G.-S., C.D., and R.F. thank the Carnot 3BCAR (project SUCRES), including the fellowship of K.G.-S. R.F. thanks the Mission for Transversal and Interdisciplinary Initiatives of the CNRS (project CASCADE). We gratefully thank N. Monties, S. Pizzut, and M. Guicherd for technical assistance in HPLC experiments, G. Cioci for assistance in DSF experiments and protein purification, and the ICEO facility dedicated to enzyme screening and discovery, part of the Integrated Screening Platform of Toulouse (PICT, IBiSA). DSF is part of the Integrated Screening Platform of Toulouse (PICT, IBiSA). We thank S. Heux and A. De Simone for the generous gift of a plasmid containing the gene encoding for FLS. J. Durand is gratefully acknowledged for his help in isolating compound 4-13C by semipreparative HPLC. P.C. thanks the Ministerio de Ciencia e Innovación (MICIN), the Fondo Europeo de Desarrollo Regional (FEDER) (grant RTI2018-094637-B-I00), and Programación Conjunta Internacional (PCI2018-092937), through the initiative ERA CoBioTech

Published
2021
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26. Impact of the Alkali Metal on the Structural and Dynamic Properties of the Anionic Pentahydride Ruthenium Complexes [M(THF) x ][RuH 5 (PCy 3 ) 2 ] (M = Li, Na, K)

Author

Ramaraj Ayyappan, Laure Vendier, Mary Grellier, Eric Clot, Sébastien Bontemps, Koushik Saha, Sylviane Sabo-Etienne, Sundargopal Ghosh, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry [Madras, Chennaï], Indian Institute of Technology Madras (IIT Madras), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), CNRS, CEFIPRA (project 5905-1), 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)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Diffraction, Anions, 010405 organic chemistry, Hydride, Dimer, Chemical structure, Organic Chemistry, chemistry.chemical_element, Group 15 compounds, 010402 general chemistry, Alkali metal, Ligands, 01 natural sciences, Ruthenium, 0104 chemical sciences, Inorganic Chemistry, Solvent, chemistry.chemical_compound, Crystallography, Monomer, chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry
Abstract

International audience; A series of anionic ruthenium pentahydride complexes with the general formula [M(THF)x][RuH5(PCy3)2] (M = Li, Na, K) were synthesized. Their characterization by multinuclear NMR, IR, X-ray diffraction, and DFT techniques show that these complexes can adopt different structural features (monomer/dimer, cis/trans phosphines, hydride/dihydrogen ligands) depending on the countercation, the solvent, and/or the temperature. While the X-ray diffraction analyses offer snapshots of three out of five isomeric structures found by DFT, the solution and solid-state NMR analysis proved that these complexes exhibit a highly dynamic behavior. Rapid H–D exchange was found between Ru–H and D2, which was attributed to the presence of Ru–H·····M interactions in the absence of crown-ether.

Published
2021
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28. Exploiting the Versatility of Phosphinobenzylsilanes for the Stabilization of 14‐Electron Rhodium(III) and Iridium(III) Complexes

Author

Sylviane Sabo-Etienne, Laure Vendier, Virginia Montiel-Palma, Julio Zamora-Moreno, María Vicky Corona-González, Miguel A. Muñoz-Hernández, Centro de Investigaciones Químicas [Morelos] (CIQ / UAEM), Universidad Autonoma del Estado de Morelos (UAEM), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), CNRS, CONACyT, and French-Mexican International Laboratory (LIA-LCMMC)

Subjects
Electron‐deficient compounds, Mixed‐valent compounds, 010405 organic chemistry, chemistry.chemical_element, Electron, Electron deficiency, Si ligands, 010402 general chemistry, Photochemistry, 01 natural sciences, P ligands, 0104 chemical sciences, Rhodium, Inorganic Chemistry, chemistry, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Iridium, 14‐Electron complexes
Abstract

International audience; Incorporating pendant silicon functionalities into phosphine ligands enables to profit from the strong σ‐electron donor and trans influence properties of Si while enhancing the coordination ability of the ligand. Herein, we show that the introduction of bulky sigma donor substituents on the Si atoms and modulation of the number of Si–H functional groups in a series of phosphinobenzylsilanes allow either the stabilization of rare highly unsaturated 14‐electron rhodium(III) and iridium(III) species devoid of agostic interactions or the access to mixed‐valence MI–MIII complexes. Our findings using isopropyl‐substituted silicon are markedly different from those obtained when employing the methyl‐substituted Si series.

Published
2019
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29. Copolymerization of ethylene with propylene and higher α-olefins catalyzed by (imido)vanadium(<scp>iv</scp>) dichloride complexes

Author

Giovanni Ricci, Giorgia Zanchin, Laure Vendier, Giuseppe Leone, Fabio Bertini, Christian Lorber, Istituto di Scienze e Tecnologie Chimiche 'Giulio Natta' (SCITEC), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), Laboratoire de chimie de coordination (LCC), 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)-Centre National de la Recherche Scientifique (CNRS), Consiglio Nazionale delle Ricerche (CNR), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Ethylene, Polymers and Plastics, Bioengineering, 010402 general chemistry, 01 natural sciences, Biochemistry, Medicinal chemistry, Catalysis, chemistry.chemical_compound, Copolymerization, Copolymer, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Methylene, Dimethylamine, 010405 organic chemistry, Chemistry, Comonomer, Organic Chemistry, Vanadium, ethylene-propylene, Polyolefins, 0104 chemical sciences, Polymerization, Propylene, Molar mass distribution
Abstract

International audience; We have synthesized and characterized a series of dimethylamine–imido V(=NR)Cl2(NHMe2)2 [R = tBu (1a), CPh3 (1b), 2,6-CHPh2-4-Cl-C6H2 (1c)], and pyridine–imido V(=NR)Cl2(Py)3 [R = tBu (2a), CPh3 (2b), 2,6-CHPh2-4-Cl-C6H2 (2c)] complexes. The solid-state structures of 1a–1c, and 2c were determined by X-ray crystallography. Complexes 1a and 2a–2c, in combination with Et2AlCl and Cl3CCO2Et, have been screened as catalysts for the copolymerization of ethylene with various α-olefins (i.e., propylene, 1-hexene, 1-octene, and 4-methyl-1-pentene). The results are compared with the known PMe2Ph–imido V(=NR)Cl2(PMe2Ph)2 [R = tBu (3a), 2,6-iPr2-C6H3 (3d)] complexes. Differences in the (co)polymerization regarding the activity and reactivity toward the target comonomers are investigated to probe the effect of imido ligand substitution, and of the coligand. With the exception of dimethylamine 1a, 2 and 3 are instantaneously activated and exhibit good activity, affording copolymers with a moderate comonomer content (4.2 < mol% < 13.7), from low to high molecular weight (36 < Mw × 103 g mol−1 < 270), and unimodal molecular weight distribution (2.1 < Mw/Mn < 2.7), strongly depending on the type of comonomer, copolymerization temperature, and, to a lesser extent, the type of ligand set employed. 13C NMR spectra of poly(ethylene-co-propylene)s have been fully interpreted as a result of uninterrupted methylene sequence distribution, the ethylene–propylene sequence, and inverted propylene units. In addition, the copolymers were characterized by DSC, TGA, and successive self-nucleation and annealing (SSA). A preliminary investigation of the tensile behavior of the copolymers was performed by uniaxial stretching until failure.

Published
2019
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31. Synthesis and Properties of Partially Saturated Fluorenyl-Derived [n]Helicenes Featuring an Overcrowded Alkene

Author

Marion Jean, Lenka Pallova, Laura Abella, Jeanne Crassous, Etienne S. Gauthier, Vincent Dorcet, Nicolas Vanthuyne, Vincent César, Laure Vendier, Stéphanie Bastin, Jochen Autschbach, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-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), Institut de Physique de Rennes (IPR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS), University at Buffalo [SUNY] (SUNY Buffalo), State University of New York (SUNY), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), This work was supported by the Agence Nationale de la Recherche (ANR-16-CE07-0019 'Hel-NHC' grant). The computational part of this research has been supported by Grant CHE-1855470 from the National Science Foundation., ANR-16-CE07-0019,HEL-NHC,Carbènes N-hétérocycliques (NHC) hélicéniques: synthèse, structure, propriétés photophysiques et activité catalytique(2016), 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)-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)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université de Rennes (UR)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Alkene, Stereochemistry, Organic Chemistry, chiroptics, Diastereomer, quantum-chemical calculations, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, Chiral resolution, 0104 chemical sciences, chemistry.chemical_compound, fluorene, Enantiopure drug, Helicene, chemistry, Intramolecular force, [CHIM]Chemical Sciences, McMurry reaction, Enantiomer, helicene
Abstract

International audience; The straightforward, multigram-scale synthesis of the partially saturated H -fluoreno[n]helicenes (n=5 or 7) featuring a central, overcrowded alkene is described. The key cyclization step was based on an intramolecular McMurry reaction from the corresponding 1,5-diketones. Chiral stationary phase HPLC analysis and isomer separation indicate that each helicenic compound is constituted of three diastereoisomers at room temperature, i. e. the configurationally stable (R,R,P)/(S,S,M) pair of enantiomers and an apparently achiral compound resulting from the rapid interconversion between the (R,S,P) and (S,R,M) enantiomers. The partially saturated H -fluoreno[n]helicenes are oxidatively aromatized to give an efficient access to the corresponding fluoreno[n]helicenes. The chiroptical properties (vibrational and electronic circular dichroism) of the chiral, enantiopure compounds have been measured and analyzed by quantum-chemical calculations, confirming their helicoidal nature.

Published
2021
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32. Synthesis and reactivity of phosphine borohydride compounds

Author

Sundargopal Ghosh, Sébastien Bontemps, Ramaraj Ayyappan, Laure Vendier, Sylviane Sabo-Etienne, Yannick Coppel, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry [Madras, Chennaï], Indian Institute of Technology Madras (IIT Madras), CNRS, and CEFIPRA (project 5905-1)

Subjects
010405 organic chemistry, Metals and Alloys, chemistry.chemical_element, General Chemistry, 010402 general chemistry, Borohydride, 01 natural sciences, Medicinal chemistry, Catalysis, 3. Good health, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry.chemical_compound, chemistry, Materials Chemistry, Ceramics and Composites, Lithium, Reactivity (chemistry), [CHIM.COOR]Chemical Sciences/Coordination chemistry, Phosphine
Abstract

International audience; Four lithium phosphine borohydride compounds featuring phenyl and naphthyl linkers have been synthesized. In-depth NMR analysis affords evidence for non-bonded through space P–B coupling. Reactivity towards CO2 leads to LiH transfer and to the quantitative formation of the corresponding ambiphilic phosphine–borane products.

Published
2021
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33. Borane-Catalysed Dinitrogen Borylation by 1,3-B–H Bond Addition

Author

Antoine Simonneau, Sébastien Bontemps, Anaïs Coffinet, Laure Vendier, Dan Zhang, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), MENESR, European Research Council (ERC) - Grant Agreement 757501 - OrFuNCo, 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), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Hydrogen bond, Ligand, Diisopinocampheylborane, Borane, 010402 general chemistry, Triple bond, 01 natural sciences, Medicinal chemistry, Borylation, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Covalent bond, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Catecholborane
Abstract

The borylation of ligated dinitrogen by 1,3-B-H bond addition over a W-N[triple bond, length as m-dash]N unit using various hydroboranes has been examined. In a previous study, we have shown that Piers' borane (1) reacted with the tungsten dinitrogen complex 2 to afford a boryldiazenido-hydrido-tungsten species. The ease and mildness of this reaction have encouraged us to extend its scope, with the working hypothesis that 1 could potentially catalyse the 1,3-B-H bond addition of other hydroboranes. Under productive reaction conditions, dicyclohexylborane (HBCy2) and diisopinocampheylborane (HBIpc2) underwent retro-hydroboration to give cyclohexylborane (H2BCy) or isopinocampheylborane (H2BIpc), respectively; these monoalkylboranes act as N2-borylating agents in the presence of a catalytic amount of 1. Under similar conditions, 9-borabicyclononane (9-BBN) slowly adds over the W-N[triple bond, length as m-dash]N unit without rearrangement to a monoalkylborane. Catecholborane (HBcat) undergoes the 1,3-B-H bond addition without the need for a catalyst. We were not able to build more than one covalent B-N bond between the terminal N of the N2 ligand and the boron reagent with this methodology.

Published
2021
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34. An anionic, chelating C(sp 3 ) / NHC ligand from the combination of N-heterobicyclic carbene and barbituric heterocycle

Author

Noël Lugan, Anna Kajetanowicz, Idir Benaissa, Laure Vendier, Stéphanie Bastin, Véronique Michelet, Karol Grela, Vincent César, Katarzyna Gajda, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Warsaw (UW), Institut de Chimie de Nice (ICN), Université Nice Sophia Antipolis (... - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA), Centre National de la Recherche Scientifique (CNRS), University Côte d’Azur, ANR-16-CE07-0006,GOLDWAR,Catalyse asymétrique en présence de complexes d'or(I) et d'or(III) – Un nouvel arsenal pour la construction d'architectures moléculaires chirales(2016), 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)-Centre National de la Recherche Scientifique (CNRS), and Université Nice Sophia Antipolis (1965 - 2019) (UNS)

Subjects
010405 organic chemistry, Chemistry, Ligand, Organic Chemistry, 010402 general chemistry, Ligands, 01 natural sciences, Medicinal chemistry, Carbon, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Alcohols, Oxidation, Chelation, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Heterocyclic compounds, Physical and Theoretical Chemistry, Carbene
Abstract

International audience; The coordination chemistry of the anionic NHC 1– based on an imidazo[1,5-a]pyridin-3-ylidene (IPy) platform substituted at the C5 position by an anionic barbituric heterocycle was studied with d6 (Ru(II), Mn(I)) and d8 (Pd(II), Rh(I), Ir(I), Au(III)) transition-metal centers. While the anionic barbituric heterocycle is planar in the zwitterionic NHC precursor 1·H, NMR spectroscopic analyses supplemented by X-ray diffraction studies evidenced the chelating behavior of ligand 1– through the carbenic and the malonic carbon atoms in all of the complexes, resulting from a deformation of the lateral barbituric heterocycle. The complexes were obtained by reaction of the free carbene with the appropriate metal precursor, except for the Au(III) complex 10, which was obtained by oxidation of the antecedent gold(I) complex [AuCl(1)]− with PhICl2 as an external oxidant. During the course of the process, the kinetic gold(I) intermediate 9 resulting from the oxidation of the malonic carbon of the barbituric moiety was isolated upon crystallization from the reaction mixture. The νCO stretching frequencies recorded for complex [Rh(1)(CO)2] (5) demonstrated the strong donating character of the malonate-C(sp3)/NHC ligand 1–. The ruthenium complex [Ru(1)Cl(p-cymene)] (11) was implemented as a precatalyst in the dehydrogenative synthesis of carboxylic acid derivatives from primary alcohols and exhibited high activities at low catalyst loadings (25–250 ppm) and a large tolerance toward functional groups.

Published
2021
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35. Electrochemical, Spectroscopic, and Computational Investigation of a Series of Polypyridyl Ruthenium(II) Complexes: Characterization of Reduced States

Author

Charlène Esmieu, Maylis Orio, Laure Vendier, Nicolas Queyriaux, Sascha Ott, Leif Hammarström, Arvind Kumar Gupta, Uppsala University, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires de Marseille (ISM2), Aix Marseille Université (AMU)-École Centrale de Marseille (ECM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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)-Centre National de la Recherche Scientifique (CNRS), and Department of Chemistry – Ångström Laboratory, UPPSALA University, Box 538, 75120, Uppsala, Sweden

Subjects
chemistry.chemical_classification, Reaction mechanism, Reactive intermediates, Series (mathematics), 010405 organic chemistry, Chemistry, Reaction mechanisms, Reactive intermediate, chemistry.chemical_element, 010402 general chemistry, Electrochemistry, 01 natural sciences, Combinatorial chemistry, Polypyridine ligands, Ruthenium, 0104 chemical sciences, Coordination complex, Characterization (materials science), Coordination chemistry, Inorganic Chemistry, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry
Abstract

International audience; A series of polypyridyl ruthenium(II) complexes has been synthesized and characterized by 1H‐NMR, electronic absorption and voltammetric techniques. Among this series, hexafluorophosphate salts of eight ruthenium(II) complexes were newly prepared. Due to the well‐known ability of this class of compounds to assist electro‐ and photocatalytic reductive processes (such as the reduction of CO2, H+ and NAD(P)+ models), particular attention has been paid to investigate the nature of their one‐ and two‐electron reduced species through computational and spectroscopic techniques.

Published
2020
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36. Reorganization of a photosensitive carbo-benzene layer in a triptych nanocatalyst with enhancement of the photocatalytic hydrogen production from water

Author

Vincent Collière, Valérie Maraval, Gérald Casterou, Laure Vendier, Yves J. Chabal, Katia Fajerwerg, Kévin Cocq, Pierre Fau, Hala Assi, Kévin Castello Lux, Remi Chauvin, Myrtil L. Kahn, Jérémy Cure, Laboratoire de chimie de coordination (LCC), 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)-Centre National de la Recherche Scientifique (CNRS), University of Texas at Dallas [Richardson] (UT Dallas), Centre National de la Recherche Scientifique (CNRS), Université de Toulouse (IDEX MUSE project), ANR-16-IDEX-0006,MUSE,MUSE(2016), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Hydrogen, Energy Engineering and Power Technology, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Silver nanoparticle, Nanomaterials, Molecule, Photocatalytic hydrogen production, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Reorganization, Hydrogen production, Plasmonic nanoparticles, Renewable Energy, Sustainability and the Environment, Titanium dioxide nanoparticles, Triptych material, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Fuel Technology, Chemical engineering, chemistry, Photocatalysis, Silver nanoparticles, 0210 nano-technology, Layer (electronics), Carbo-benzene dye
Abstract

International audience; The preparation of a triptych nanomaterial made of TiO2 nanoparticles as semiconductor, Ag plasmonic nanoparticles and a carbo-benzene macrocyclic molecule as photosensitizer is described, and used to produce hydrogen by photo-reduction of pure deionized water under 2.2 bar argon pressure without any electrical input. Silver nanoparticles (~5 nm) are grafted onto the surface of commercial TiO2 nanoparticles (~23 nm) by a photo-deposition process using an original silver amidinate precursor. The thickness of the photosensitive layer (2 nm), which completes the assembly, plays a crucial role in the efficiency and robustness of the triptych nanocatalyst. Thanks to the organic layer reorganization during the first ~24 h of irradiation, it leads to an enhancement of the hydrogen production rate up to 5 times. The amount of silver and carbo-benzene are optimized, along with the mass concentration of nanocatalyst in water and the pH of the aqueous medium, to allow reaching a hydrogen production rate of 22.1 μmol·h−1·gphotocatalyst−1.

Published
2020
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37. Topological Analysis of Ag–Ag and Ag–N Interactions in Silver Amidinate Precursor Complexes of Silver Nanoparticles

Author

Pierre Fau, Emilie Lebon, Myrtil L. Kahn, Laure Vendier, Christine Lepetit, Maxime Puyo, Katia Fajerwerg, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS), and Ministère de l’Enseignement Supérieur, de la Recherche et de l’Innovation (MESRI)

Subjects
Silver-amidinate complexes, Argentophilic interaction, 010405 organic chemistry, Chemistry, Substituent, 010402 general chemistry, Topology, 01 natural sciences, Dissociation (chemistry), Silver nanoparticle, 0104 chemical sciences, Ion, law.invention, ELF and QTAIM topological analyses, Inorganic Chemistry, chemistry.chemical_compound, Chemical bond, law, Covalent bond, Intramolecular force, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Crystallization, Metal-metal bond
Abstract

International audience; A series of silver amidinate complexes has been studied both experimentally and theoretically, in order to investigate the role of the precursor complex in the control of the synthesis of silver nanoparticles via an organometallic route. The replacement of the methyl substituent of the central carbon atom of the amidinate anion by a n-butyl group allows for the crystallization of the tetranuclear silver amidinate complex 3 instead of a mixture of di- and trinuclear silver amidinate complexes 1 and 2, as obtained with a methyl substituent. The relative stabilities and dissociation schemes of various isomeric arrangements of silver atoms in 3 are investigated at the computational DFT level of calculation, depending on the substituents of the amidinate ligand. The tetranuclear silver amidinate complex 4, exhibiting a diamondlike arrangement of the four silver atoms, is also considered. Ag–N bonds and argentophilic Ag–Ag interactions are finely characterized using ELF and QTAIM topological analyses and compared over the series of the related di-, tri-, and tetranuclear silver amidinate complexes 1–4. In contrast to the Ag–N dative bonds very similar over the series, argentophilic Ag–Ag interactions of various strengths and covalence degree are characterized for complexes 1–4. This gives insight into the role of the amidinate substituents on the nuclearity and intramolecular chemical bonding of the silver amidinate precursors, required for the synthesis of dedicated AgNPs with chemically well defined surfaces.

Published
2020
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38. Role of the Main and Auxiliary Ligands in the Nuclearity of Cu-Ln Complexes

Author

Maria‐Jesus Rodriguez Douton, Jean-Pierre Costes, Laure Vendier, Sergiu Shova, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), National Enterprise for nanoScience and nanoTechnology (NEST), Scuola Normale Superiore di Pisa (SNS)-Scuola Universitaria Superiore Sant'Anna [Pisa] (SSSUP)-Istituto Italiano di Tecnologia (IIT)-Consiglio Nazionale delle Ricerche [Pisa] (CNR PISA), and 'Petru Poni' Institute of Macromolecular Chemistry

Subjects
Lanthanide, chemistry.chemical_classification, 010405 organic chemistry, Chemistry, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Copper, 0104 chemical sciences, Coordination complex, Inorganic Chemistry, Crystallography, X-ray crystallography, [CHIM.COOR]Chemical Sciences/Coordination chemistry
Abstract

International audience; Trianionic ligands with an inner N2O2, an outer O2O2 or O2O coordination site and an oxygen atom coming from an amide function not involved in these sites yield dinuclear Cu-Ln complexes that self-assemble into tetranuclear species with an alternate arrangement of Cu and Ln ions. This alternate Cu-Gd arrangement impedes Cu–Cu and Gd-Gd interactions that could be antiferromagnetic and favours ferromagnetic Cu-Gd interactions whose strength depends on the nature of the bridge, the phenoxo bridge made of a single oxygen atom or the amidato bridge made of three NCO atoms. Depending on the ligands, the phenoxo bridges can be single (CuOGd) or double (CuO2Gd), while the amidato bridge is always a single (CuNCOGd) bridge. A particular complex involving a trinuclear Cu-Gd-Cu arrangement through two amidato bridges confirms that the Cu-Gd interaction through the amidato bridge is always weaker than the interaction through the phenoxo bridge. It has been possible to obtain complexes with an alternate Cu-Gd arrangement involving more than two Cu-Gd entities when two amidato bridges are present. These two amidato bridges may come from a main ligand, as in the case of tetraanionic ligands possessing two amide functions, or from two different ligands involving one amide function that are assembled by a Gd ion through their phenoxo functions. Note that the presence of auxiliary ligands with a good chelating ability for the Gd ion, such as the diketonato ligands, allows isolation of tetranuclear species only, regardless of the number of amide functions.

Published
2020
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39. Bis[diphenylphosphino]methane and its bridge-substituted analogues as chemically non-innocent ligands for H

Author

Nikolay V, Kireev, Oleg A, Filippov, Ekaterina S, Gulyaeva, Elena S, Shubina, Laure, Vendier, Yves, Canac, Jean-Baptiste, Sortais, Noël, Lugan, and Dmitry A, Valyaev

Abstract

Deprotonation of fac-[(κ2P,P-Ph2PCH(R)PPh2)Mn(CO)3Br] (R = H, Me, Ph) produces the corresponding diphosphinomethanide derivatives fac-[(κ3P,C,P-Ph2PC(R)PPh2)Mn(CO)3], which are prone to activate H2 to form the hydride complexes fac-[(κ2P,P-Ph2PCH(R)PPh2)Mn(CO)3H]. The substitution of the dppm bridge improves dramatically the reaction efficiency and this was rationalized by DFT calculations.

Published
2020

40. Regioselective C–F Bond Activation/C–C Bond Formation between Fluoropyridines and Cyclopropyl Groups at Zirconium

Author

Laure Vendier, Anthony Pujol, Natalie Crespo, Nuria Romero, Michel Etienne, Quentin Dufrois, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), MENESR, CONACYT, and ANR-11-BS-07-009-2

Subjects
Inert, Zirconium, 010405 organic chemistry, Bond, Organic Chemistry, chemistry.chemical_element, Regioselectivity, Bond formation, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Inorganic Chemistry, Reaction sequence, chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry
Abstract

International audience; This paper addresses the problem of the strong and inert C–F bond activation of various fluoropyridines by zirconocene derivatives. Dicyclopropylzirconocene, [Cp2Zr(c-C3H5)2], thermally eliminates cyclopropane, giving the transient intermediate zirconabicyclobutane [Cp2Zr(η2-c-C3H4)] that cleaves a C–F bond of pentafluoropyridine selectively at position 2, forming new Zr–F and C–C bonds stereoselectively to give [Cp2ZrF{c-cis-CHCH2CH(2-NC5F4)}]. DFT computations indicate the selectivity results from the initial formation of an azazirconacycle intermediate that undergoes ring opening and C–F bond cleavage. Transmetalation with a variety of cyclopropyl donors yields [Cp2Zr(c-C3H5){c-cis-CHCH2CH(2-NC5F4)}] with the selectivity depending on the nature of the donor. A synthetic cycle is realized when [Cp2Zr(c-C3H5){c-cis-CHCH2CH(2-NC5F4)}] reacts with pentafluoropyridine, yielding 2-(c-C3H5)NC5F4 and [Cp2ZrF{c-cis-CHCH2CH(2-NC5F4)}] with C–F bond activation. Attempts at converting this reaction sequence to a catalytic version failed due to either decomposition of the active species or multiple C–F bond substitutions by the transmetalating agent.

Published
2020
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41. Reaction of Methyllithium with Group 6 Phosphine Dinitrogen Complexes

Author

Laure Vendier, Christian Bijani, Antoine Simonneau, Michel Etienne, Amal Bouammali, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), European Research Council (ERC) - Grant Agreement 757501 - OrFuNCo, National Center for Scientific Research (CNRS), 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), and Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, chemistry.chemical_element, Tungsten, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, 3. Good health, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Group (periodic table), Molybdenum, Methyllithium, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Phosphine
Abstract

International audience; The reaction of MeLi with several group 6 phosphine end-on dinitrogen complexes of the general formula [ML4(N2)2] (M = Mo or W) is reported. Unlike the isoelectronic complex [CpMn(CO)2(N2)] on which RLi reagents have been reported to add to the N2 ligand, we show herein that MeLi attacks the metal centre to afford rare anionic trans methyl dinitrogen complexes.

Published
2020
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42. Asymmetric transfer hydrogenation of ketones promoted by manganese(I) pre-catalysts supported by bidentate aminophosphines

Author

Jean-Baptiste Sortais, Laure Vendier, Stéphanie Bastin, Antoine Bruneau-Voisine, Karim Azouzi, Laboratoire de chimie de coordination (LCC), 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)-Centre National de la Recherche Scientifique (CNRS), 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), Institut Universitaire de France, IUFAgence Nationale de la Recherche, ANR ANR-15- CE07‐0001Centre National de la Recherche Scientifique, CNRSInstitut Universitaire de France, IUFCentre National de la Recherche Scientifique, CNRSUniversité de Rennes 1Agence Nationale de la Recherche, ANR ANR-15-CE07-001Centre National de la Recherche Scientifique, CNRS, ANR-15-CE07-0001,Ferracycles,Synthèse et application en catalyse de complexes cyclométalés du fer obtenus par activation C-H(2015), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)

Subjects
Manganese, Denticity, Hydrogen, 010405 organic chemistry, Chemistry, Ligand, Process Chemistry and Technology, organic chemicals, chemistry.chemical_element, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Ketones, 010402 general chemistry, Transfer hydrogenation, 01 natural sciences, Medicinal chemistry, Catalysis, 0104 chemical sciences, Chiral aminophosphine ligands, heterocyclic compounds, Enantiomer, Reduction
Abstract

International audience; A series of commercially available chiral amino-phosphines, in combination with Mn(CO)5Br, has been evaluated for the asymmetric reduction of ketones, using isopropanol as hydrogen source. With the most selective ligand, the corresponding manganese complex was synthesized and fully characterized. A series of ketones (20 examples) was hydrogenated in the presence of 0.5 mol% of the manganese pre-catalyst at 30 °C, affording the chiral alcohols in high yields with enantiomeric excesses up to 99%.

Published
2020
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43. Role of the kinetic template effect in the preparation of an original copper complex

Author

Carine Duhayon, Jean-Pierre Costes, Laure Vendier, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
chemistry.chemical_classification, 010405 organic chemistry, Ligand, Imine, chemistry.chemical_element, Protonation, 010402 general chemistry, 01 natural sciences, Aldehyde, Copper, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Amide, Polymer chemistry, Diethylenetriamine, Materials Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Amine gas treating, Physical and Theoretical Chemistry
Abstract

International audience; Reaction of diethylenetriamine with phenol derivatives possessing a phenyl ester function yields a ligand corresponding to the monocondensation of diethylenetriamine with the phenol derivative. In a following step, its coordination to copper ions gives a neutral complex that is able to react with orthovanillin in order to yield an original complex made of a non symmetric ligand possessing three nitrogen, amide, imine and secondary amine, and four oxygen, amide, phenol (2) and methoxy donor atoms, thanks to the kinetic template effect. In our example, the copper center brings the three reactive functions (first primary amine and aldehyde, then amide) in close vicinity so that the formation of an imine function and the protonation of the amide function can occur. The structural determination of the resulting complex confirms an unexpected copper coordination.

Published
2018
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44. Triangles and Squares for a Unique Molecular Crystal Structure: Unsupported Two-Coordinate Lithium Cations and CC Agostic Interactions in Cyclopropyllithium Derivatives

Author

Michel Etienne, Quentin Dufrois, Laure Vendier, Chiara Dinoi, Jean-Claude Daran, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées

Subjects
Agostic interaction, Coordination sphere, Trimethylsilyl, Chemistry, 010405 organic chemistry, chemistry.chemical_element, General Chemistry, Crystal structure, General Medicine, 010402 general chemistry, 01 natural sciences, Catalysis, Cyclopropane, 0104 chemical sciences, chemistry.chemical_compound, Crystallography, Lithium, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Lewis acids and bases, Organometallic chemistry
Abstract

International audience; Understanding and controlling the aggregation state is germane to alkyllithium chemistry. Lewis base-free alkyllithium compounds normally form tetrahedral tetramers or octahedral hexamers in the solid state with the lithium cations being three-coordinate. We report that the unsupported cyclopropyl derivative 1-(trimethylsilyl)cyclopropyllithium [μ-c-C(SiMe3)C2H4Li]4 (1), synthesized by the reduction of 1-(phenylthio)-1-(trimethylsilyl)cyclopropane, crystallizes as a tetramer in the space group I-4 with the two-coordinate lithium atoms forming a square. CC agostic interactions complete the coordination sphere around each lithium. The aggregate is preserved in hydrocarbon solution. Furthermore, CC agostic interactions compete intra- and intermolecularly with Lewis base donation as in the unsaturated dimer of 1-(phenylthio)cyclopropyllithium [Li(thf)2μ-c-C(SPh)C2H42Li (thf)] (3) which is also fully characterized.

Published
2017
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45. Coupling and Dearomatization of Pyridines at a Transient η2 -Cyclopropene/Bicyclobutane Zirconocene Complex

Author

Chiara Dinoi, Laure Vendier, Michel Etienne, Quentin Dufrois, Nuria Romero, Laboratoire de chimie de coordination (LCC), Institut de Chimie de Toulouse (ICT-FR 2599), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche pour le Développement (IRD)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées, Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), 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)-Centre National de la Recherche Scientifique (CNRS), 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), 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 sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), and Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
pyridine, [PHYS]Physics [physics], 010405 organic chemistry, Stereochemistry, Ligand, Organic Chemistry, zirconium, General Chemistry, cyclopropene, coupling reactions, Cyclopropene, 010402 general chemistry, 01 natural sciences, Catalysis, Coupling reaction, 0104 chemical sciences, Cyclopropane, chemistry.chemical_compound, Stereospecificity, chemistry, Pyridine, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Selectivity, cyclopropyl, Bicyclobutane
Abstract

bibtex: ISI:000414633200027 bibtex\location:'POSTFACH 101161, 69451 WEINHEIM, GERMANY',publisher:'WILEY-V C H VERLAG GMBH',type:'Article',affiliation:'Etienne, M (Reprint Author), CNRS, LCC, 205 Route Narbonne,BP44099, F-31077 Toulouse, France. Etienne, M (Reprint Author), Univ Toulouse, UPS, INPT, LCC, F-31077 Toulouse, France. Romero, Nuria; Dufrois, Quentin; Vendier, Laure; Dinoi, Chiara; Etienne, Michel, CNRS, LCC, 205 Route Narbonne,BP44099, F-31077 Toulouse, France. Romero, Nuria; Dufrois, Quentin; Vendier, Laure; Dinoi, Chiara; Etienne, Michel, Univ Toulouse, UPS, INPT, LCC, F-31077 Toulouse, France. Romero, Nuria, Univ Autonoma Barcelona, Dept Quim, Cerdanyola Del Valles Ba 08193, Spain. Dinoi, Chiara, LPCNO INSA, 135 Ave Rangueil, F-31077 Toulouse, France.','author-email':'michel.etienne@lcc-toulouse.fr',da:'2018-12-05','doc-delivery-number':'FM0EI',eissn:'1521-3765','funding-acknowledgement':'MENESR [ANR-11-BS07-0009]; COST Action CHAOS [CA15106]','funding-text':'We thank the MENESR for a PhD grant to QD, the ANR (Green-LAkE project; ANR-11-BS07-0009) and COST Action CHAOS (CA15106) for support.','journal-iso':'Chem.-Eur. J.','keywords-plus':'AROMATIC N-HETEROCYCLES; CH BOND ACTIVATION; CRYSTAL-STRUCTURES; ALKYL COMPLEXES; H BONDS; METAL; CHEMISTRY; ETA(2)-CYCLOPROPENE; ORGANOZIRCONIUM; NIOBIUM','number-of-cited-references':'42','orcid-numbers':'Romero, Nuria/0000-0002-2704-7779 Vendier, Laure/0000-0002-7111-9258 Etienne, Michel/0000-0002-1099-3232','research-areas':'Chemistry','researcherid-numbers':'Romero, Nuria/A-9756-2016','times-cited':'0','unique-id':'ISI:000414633200027','usage-count-last-180-days':'4','usage-count-since-2013':'12','web-of-science-categories':'Chemistry, Multidisciplinary'\; International audience; This paper reports on stereospecific coupling reactions between an (2)-cyclopropene ligand and pyridine derivatives, which are preferred to alternative C-H bond activation reactions. The dicyclopropylzirconocene complex [Cp2Zr(c-C3H5)(2)](1) eliminates cyclopropane to generate the (2)-cyclopropene/bicyclobutane intermediate [Cp2Zr((2)-c-C3H4)](A). A does not activate any pyridine C-H bonds, but rather pyridine inserts into a Zr-C bond of A, yielding an azazirconacycle with a dearomatized pyridyl group [Cp2Zr\(2)-N,C-8-(2-c-C3H4)-C5H5N\](2). Kinetic data, isotopelabelling experiments, and DFT calculations indicate that the rate-determining step of this stereospecific reaction is cyclopropane elimination, and that the stability of the intermediate [Cp2Zr((2)-c-C3H4)(NC5H5)](A-py) governs the selectivity of the reaction. Complex2 tautomerizes to [Cp2Zr\(2)-N,C-8-(2-C3H5)-C5H4N\](6) through a base-catalyzed proton migration accompanied by cyclopropyl opening and restoration of conjugation within the zirconacycle.

Published
2017
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46. Highly Fluorinated Tris(indazolyl)borate Hydrocarbyl Complexes of Calcium and Magnesium: Synthesis and Structural Studies

Author

Michel Etienne, Quentin Dufrois, Laure Vendier, Nuria Romero, Chiara Dinoi, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées

Subjects
Agostic interaction, 010405 organic chemistry, Ligand, Magnesium, Acetylide, Organic Chemistry, Inorganic chemistry, chemistry.chemical_element, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, Salt metathesis reaction, Molecule, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Boron
Abstract

International audience; Heteroleptic phenylacetylide complexes [F12-Tp4Bo,3PhAe(C≡CPh)]x of calcium (Ae = Ca, x = 2; 2) and magnesium (Ae = Mg, x = 1; 4) containing the highly fluorinated 3-phenyl hydrotris(indazolyl)borate F12-Tp4Bo,3Ph− ligand have been synthesized by acid–base reactions between the corresponding silylamido derivatives [F12-Tp4Bo,3PhAeN(SiRMe2)2] (R = Me, Ae = Ca (1); R = H, Ae = Mg (3)) and PhC≡CH. Compounds 2 and 4 have been characterized by NMR spectroscopy and X-ray diffraction analysis. 2 crystallizes as a dinuclear complex, showing two nonsymmetrical “side-on” (π-type) interactions between the acetylide units and the Ca centers, whereas 4 crystallizes as a mononuclear complex, displaying a four-coordinate magnesium. The molecular structure of the complex [F12-Tp4Bo,3PhMgN(SiMe2H)2] (3), obtained by the salt metathesis reaction between [MgN(SiMe2H)22] and [TlF12-Tp4Bo,3Ph], is also reported. 3 is also four-coordinate and exhibits a Mg···β-Si–H agostic distortion. The synthesis and in situ characterization of the heteroleptic alkyl complex [F12-Tp4Bo,3PhCaCH(SiMe3)2(THF)] (5) is also reported, although attempts to isolate this compound failed due to its extreme sensitivity to temperature.

Published
2017
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47. Cytotoxic Vanadium Complexes of Branched [ONNO]‐Type Diamine Bis(phenolato) Ligands

Author

Christian Lorber, Laure Vendier, Edit Y. Tshuva, Gilad Nahari, Lilia Reytman, Institute of Chemistry, The Hebrew University of Jerusalem, The Hebrew University of Jerusalem (HUJ), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Vanadium, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Diamine, Polymer chemistry, Organic chemistry, Cytotoxic T cell, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Cytotoxicity
Abstract

International audience; Vanadium complexes are attractive potential alternatives to platinum-based anticancer drugs. Two vanadium(V) complexes, based on a common chelating tetradentate diaminobis(phenolato) ligand featuring a branched connectivity but differing in their labile ligands, were synthesized and characterized. Whereas the isopropoxido complex was obtained as a mixture of cis and trans isomers with regard to the orientation of the labile group vs. the amine sidearm, the salicylato-containing complex was obtained as a single trans isomer. X-ray structures of the complexes featured octahedral geometry for both. The two complexes exhibited high cytotoxic activity toward different cancer cells, often higher than that of cisplatin, including toward cisplatin-resistant ovarian cancer cells. These complexes demonstrated rapid hydrolysis, releasing the labile ligand within several minutes, with no indications of release of free chelating ligand after water exposure, suggesting that polynuclear hydrolysis products are involved in the cellular activity.

Published
2017
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48. Solvatomorphism and structural-spin crossover property relationship in bis[hydrotris(1,2,4-triazol-1-yl)borate]iron(<scp>ii</scp>)

Author

Gábor Molnár, Karl Ridier, Sylvain Rat, Azzedine Bousseksou, Lionel Salmon, Laure Vendier, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), and Université Fédérale Toulouse Midi-Pyrénées

Subjects
Spin states, Chemistry, Spin transition, 02 engineering and technology, General Chemistry, Crystal structure, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, Magnetic susceptibility, 0104 chemical sciences, Bond length, Crystallography, Spin crossover, [CHIM.COOR]Chemical Sciences/Coordination chemistry, General Materials Science, Orthorhombic crystal system, Isostructural, 0210 nano-technology
Abstract

International audience; Two solvatomorphs of the mononuclear bis[hydrotris(1,2,4-triazol-1-yl) borate] iron(II) complex, [Fe(HB(tz)(3))(2)] (1) and [Fe(HB(tz)(3))(2)]center dot 6H(2)O (1 center dot 6H(2)O), were obtained by modifying the nature of the crystallization solvent. The crystal structure, thermal stability and spin crossover properties of the crystals and associated bulk powder samples were analysed using variable-temperature single-crystal and powder X-ray diffraction, thermogravimetry, calorimetry, and Raman and Fe-57 Mossbauer spectroscopy as well as by means of magnetic susceptibility and optical microscopy measurements. The orthorhombic (Cmca) solvatomorph 1 center dot 6H(2)O loses water between ca. 323-353 K, leading to the disintegration of the crystals into the polycrystalline sample 1. The solvent-free crystals of 1 crystallize in the orthorhombic space group Pbca with half a complex molecule in the asymmetric unit. They exhibit a remarkably abrupt phase transition around 334 K between the high spin and low spin states. This (isostructural) spin transition is accompanied by a nearly isotropic change of the Fe-II -N bond lengths (8.3 perpendicular to 0.5%) and a highly anisotropic unit cell volume change (4.6 +/- 0.1%). The very high cooperativity of the spin transition in 1 (Gamma = 5700 +/- 50 J mol(-1)) is rather unusual in mononuclear SCO compounds. This property can be related to the relatively high stiffness of the lattice (Debye temperature theta(D) = 198 +/- 2 K), which involves numerous C-H center dot center dot center dot N hydrogen contacts between each molecule with fourteen neighboring molecules.

Published
2017
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49. Supramolecular organization of perfluorinated 1H-indazoles in the solid state using X-ray crystallography, SSNMR and sensitive (VCD) and non sensitive (MIR, FIR and Raman) to chirality vibrational spectroscopies

Author

Kane Jacob, Juan Jesús López-González, María Mar Quesada-Moreno, José Elguero, Ibon Alkorta, Rosa M. Claramunt, Juan Ramón Avilés-Moreno, Michel Etienne, Laure Vendier, Ministerio de Economía y Competitividad (España), Junta de Andalucía, Comunidad de Madrid, European Commission, Grupo de Investigacion Quimica Fisica Teorica y Experimental (FQM-173), Departamento de Quimica Fisica y Analitica, Facultad de Ciencias Experimentales, Universidad de Jaen, Universidad de Jaén (UJA), Departamento de Sistemas Fisicos, Quimicos y Naturales, Facultad de Ciencias Experimentales, Universidad Pablo de Olavide, Universidad Pablo de Olavide [Sevilla] (UPO), Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées, Instituto de Quimica Médica (CSIC), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Departamento de Quimica Organica y Bio-Organica, Facultad de Ciencias, Universidad Nacional de Educacion a Distancia, and Universidad Nacional de Educación a Distancia (UNED)

Subjects
010405 organic chemistry, Chemistry, Supramolecular chemistry, General Physics and Astronomy, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Crystallography, symbols.namesake, Solid-state nuclear magnetic resonance, Helix, X-ray crystallography, symbols, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Enantiomer, Enantiomeric excess, Chirality (chemistry), Raman spectroscopy
Abstract

1H-Indazole derivatives exhibit a remarkable property since some of them form chiral supramolecular structures starting from achiral monomers. The present work deals with the study of three perfluorinated 1H-indazoles that resolve spontaneously as conglomerates. These conglomerates can contain either a pure enantiomer (one helix) or a mixture of both enantiomers (both helices) with an enantiomeric excess (e.e.) of one of them. The difficulty of the structural analysis of these types of compounds is thus clear. We outline a complete strategy to determine the structures and configurations (M or P helices) of the enantiomers (helices) forming the conglomerates of these perfluorinated 1H-indazoles based on X-ray crystallography, solid state NMR spectroscopy and different solid state vibrational spectroscopies that are either sensitive (VCD) or not (FarIR, IR and Raman) to chirality, together with quantum chemical calculations (DFT)., This work was carried out with financial support from the Ministerio de Economía y Competitividad (Project No. CTQ2014- 56833R and CTQ2015-63997-C2-2-P), CICE/Junta de Andalucía (P08-FQM-04096) and CICE/JA-FEDER-UJA: Plan de Fortalecimiento de las Capacidades de I+D+i/2014-15 (UJA2013/08/03) and Comunidad Autónoma de Madrid (Project FOTOCARBON, ref. S2013/MIT-2841). Computer, storage and other resources from the CTI (CSIC) are gratefully acknowledged. Authors thank the University of Jaén for continuing financial support, for bridge projects (UJA2015/08/07) and (UJA2016/08/15) and for Accion 2: Financiacion de Incentivos a la Excelencia de I+D+i de la UJA 2014-15 in 2014 and 2015 calls and to its CICT for instrumental facilities. Authors also thank the FQM-323 research group, especially Rafael Lopez Blanco, David Moreno Gonzalez and Jose Robles Molina, for their help in the laboratory. M. M. Q. M. thanks the University of Jaen for a pre-doctoral fellowship. The CNRS is acknowledged for support

Published
2017
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50. Frustrated Lewis Pair Chemistry Enables N2 Borylation by Formal 1,3‐Addition of a B−H Bond in the Coordination Sphere of Tungsten

Author

Michel Etienne, Antoine Simonneau, David Specklin, Anaïs Coffinet, Laure Vendier, Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées, MENESR, CNRS, ERC - OrFuNCo - Grant agreement ID: 757501, 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)-Centre National de la Recherche Scientifique (CNRS), and Université de Toulouse (UT)

Subjects
Coordination sphere, 010405 organic chemistry, Hydrogen bond, Hydride, Organic Chemistry, General Chemistry, Borane, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Borylation, Medicinal chemistry, Catalysis, Frustrated Lewis pair, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Electrophile, [CHIM]Chemical Sciences, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Lewis acids and bases
Abstract

International audience; Dedicated to Professor Max Malacria on the occasion of his 70 th birthday. Abstract: The first example of a formal 1,3-B-H bond addition across the M-N≡N unit of an end-on dinitrogen complex 5 has been achieved. The use of Piers' borane HB(C6F5)2 1 was essential to observe this reactivity and it plays a triple role in this transformation: i) electrophilic N2-borylation agent, ii) Lewis acid in a frustrated Lewis pair-type B-H bond activation and iii) hydride shuttle to the metal center. This chemistry is supported by NMR and solid-state characterization of products and intermediates. The combination of chelate effect and strong sigma donation in the diphosphine depe ligand was mandatory to avoid phosphine dissociation that otherwise led to complexes where borylation of N2 occurred without hydride transfer.

Published
2019
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