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20 results on '"Del rosal, Iker"'

1. CO 2 cleavage by tantalum/M (M = iridium, osmium) heterobimetallic complexes

Author

Lachguar, Abdelhak, Ye, Christopher Z, Kelly, Sheridon N, Jeanneau, Erwann, Del Rosal, Iker, Maron, Laurent, Veyre, Laurent, Thieuleux, Chloé, Arnold, John, and Camp, Clément

Subjects
Inorganic Chemistry, Chemical Sciences, Organic Chemistry, Chemical sciences, Engineering
Abstract

A novel Ta/Os heterobimetallic complex, [Ta(CH2tBu)3(μ-H)3OsCp*], 2, is prepared by protonolysis of Ta(CHtBu)(CH2tBu)3 with Cp*OsH5. Treatment of 2 and its iridium analogue [Ta(CH2tBu)3(μ-H)2IrCp*], 1, with CO2 under mild conditions reveal the efficient cleavage of CO2, driven by the formation of a tantalum oxo species in conjunction with CO transfer to the osmium or iridium fragments, to form Cp*Ir(CO)H2 and Cp*Os(CO)H3, respectively. This bimetallic reactivity diverges from more classical CO2 insertion into metal-X (X = metal, hydride, alkyl) bonds.

Published
2024

2. Photolysis-driven bond activation by thorium and uranium tetraosmate polyhydride complexes

Author

Ye, Christopher Z, Del Rosal, Iker, Kelly, Sheridon N, Brackbill, I Joseph, Maron, Laurent, Camp, Clément, and Arnold, John

Subjects
Inorganic Chemistry, Chemical Sciences, Chemical sciences
Abstract

Transition metal multimetallic complexes have seen intense study due to their unique bonding and potential for cooperative reactivity, but actinide-transition metal (An-TM) species are far less understood. We have synthesized uranium- and thorium-osmium heterometallic polyhydride complexes in order to study An-Os bonding and investigate the reactivity of An-Os interactions. Computational studies suggest the presence of a significant bonding interaction between the actinide center and the four coordinated osmium centers supported by bridging hydrides. Upon photolysis, these complexes undergo intramolecular C-H activation with the formation of an Os-Os bond, while the thorium complex may activate an additional C-H bond of the benzene solvent, resulting in a μ-η1,η1 phenyl ligand across one Th-Os interaction.

Published
2024

3. A versatile strategy for the formation of hydride-bridged actinide–iridium multimetallics

Author

Ye, Christopher Z, Del Rosal, Iker, Boreen, Michael A, Ouellette, Erik T, Russo, Dominic R, Maron, Laurent, Arnold, John, and Camp, Clément

Subjects
Inorganic Chemistry, Chemical Sciences, Chemical sciences
Abstract

Reaction of the potassium pentamethylcyclopentadienyl iridate tris-hydride K[IrCp*H3] with UCl4 and ThCl4(DME)2 led to the complete replacement of the halide ligands to generate multimetallic complexes U{(μ-H)3IrCp*}4 (1) and Th{[(μ-H2)(H)IrCp*]2[(μ-H)3IrCp*]2} (2), respectively. These analogues feature a significant discrepancy in hydride bonding modes; 1 contains twelve bridging hydrides while 2 contains ten bridging hydrides and two terminal, Ir-bound hydrides. Use of a U(iii) starting material, UI3(1,4-dioxane)1.5, resulted in the octanuclear complex {U[(μ2-H3)IrCp*]2[(μ3-H2)IrCp*]}2 (3). Computational studies indicate significant bonding character between U/Th and Ir in 1 and 2, with f-orbital involvement in the singly-occupied molecular orbitals of the uranium species 1. In addition, these studies attribute the variation in hydride bonding between 1 and 2 to differences in dispersion effects.

Published
2023

4. A Uranium(II) Arene Complex That Acts as a Uranium(I) Synthon

Author

Straub, Mark D, Ouellette, Erik T, Boreen, Michael A, Britt, R David, Chakarawet, Khetpakorn, Douair, Iskander, Gould, Colin A, Maron, Laurent, Del Rosal, Iker, Villarreal, David, Minasian, Stefan G, and Arnold, John

Subjects
Inorganic Chemistry, Chemical Sciences, Coordination Complexes, Density Functional Theory, Ligands, Models, Chemical, Oxidation-Reduction, Thorium, Uranium, CSD-46-All CSGB, General Chemistry, Chemical sciences, Engineering
Abstract

Two-electron reduction of the amidate-supported U(III) mono(arene) complex U(TDA)3 (2) with KC8 yields the anionic bis(arene) complex [K[2.2.2]cryptand][U(TDA)2] (3) (TDA = N-(2,6-di-isopropylphenyl)pivalamido). EPR spectroscopy, magnetic susceptibility measurements, and calculations using DFT as well as multireference CASSCF methods all provide strong evidence that the electronic structure of 3 is best represented as a 5f4 U(II) metal center bound to a monoreduced arene ligand. Reactivity studies show 3 reacts as a U(I) synthon by behaving as a two-electron reductant toward I2 to form the dinuclear U(III)-U(III) triiodide species [K[2.2.2]cryptand][(UI(TDA)2)2(μ-I)] (6) and as a three-electron reductant toward cycloheptatriene (CHT) to form the U(IV) complex [K[2.2.2]cryptand][U(η7-C7H7)(TDA)2(THF)] (7). The reaction of 3 with cyclooctatetraene (COT) generates a mixture of the U(III) anion [K[2.2.2]cryptand][U(TDA)4] (1-crypt) and U(COT)2, while the addition of COT to complex 2 instead yields the dinuclear U(IV)-U(IV) inverse sandwich complex [U(TDA)3]2(μ-η8:η3-C8H8) (8). Two-electron reduction of the homoleptic Th(IV) amidate complex Th(TDA)4 (4) with KC8 gives the mono(arene) complex [K[2.2.2]cryptand][Th(TDA)3(THF)] (5). The C-C bond lengths and torsion angles in the bound arene of 5 suggest a direduced arene bound to a Th(IV) metal center; this conclusion is supported by DFT calculations.

Published
2021

8. The Nature of Secondary Interactions at Electrophilic Metal Sites of Molecular and Silica-Supported Organolutetium Complexes from Solid-State NMR Spectroscopy

Author

Conley, Matthew P, Lapadula, Giuseppe, Sanders, Kevin, Gajan, David, Lesage, Anne, del Rosal, Iker, Maron, Laurent, Lukens, Wayne W, Copéret, Christophe, and Andersen, Richard A

Subjects
Inorganic Chemistry, Chemical Sciences, General Chemistry, Chemical sciences, Engineering
Abstract

Lu[CH(SiMe3)2]3 reacts with [SiO2-700] to give [(≡SiO)Lu[CH(SiMe3)2]2] and CH2(SiMe3)2. [(≡SiO)Lu[CH(SiMe3)2]2] is characterized by solid-state NMR and EXAFS spectroscopy, which show that secondary Lu···C and Lu···O interactions, involving a γ-CH3 and a siloxane bridge, are present. From X-ray crystallographic analysis, the molecular analogues Lu[CH(SiMe3)2]3-x[O-2,6-tBu-C6H3]x (x = 0-2) also have secondary Lu···C interactions. The (1)H NMR spectrum of Lu[CH(SiMe3)2]3 shows that the -SiMe3 groups are equivalent to -125 °C and inequivalent below that temperature, ΔG(⧧)(Tc = 148 K) = 7.1 kcal mol(-1). Both -SiMe3 groups in Lu[CH(SiMe3)2]3 have (1)JCH = 117 ± 1 Hz at -140 °C. The solid-state (13)C CPMAS NMR spectrum at 20 °C shows three chemically inequivalent resonances in the area ratio of 4:1:1 (12:3:3); the J-resolved spectra for each resonance give (1)JCH = 117 ± 2 Hz. The (29)Si CPMAS NMR spectrum shows two chemically inequivalent resonances with different values of chemical shift anisotropy. Similar observations are obtained for Lu[CH(SiMe3)2]3-x[O-2,6-tBu-C6H3]x (x = 1 and 2). The spectroscopic data point to short Lu···Cγ contacts corresponding to 3c-2e Lu···Cγ-Siβ interactions, which are supported by DFT calculations. Calculated natural bond orbital (NBO) charges show that Cγ carries a negative charge, while Lu, Hγ, and Siβ carry positive charges; as the number of O-based ligands increases so does the positive charge at Lu, which in turns shortens the Lu···Cγ distance. The change in NBO charges and the resulting changes in the spectroscopic and crystallographic properties show how ligands and surface-support sites rearrange to accommodate these changes, consistent with Pauling's electroneutrality concept.

Published
2016

10. Mechanistic Investigations via DFT Support the Cooperative Heterobimetallic C-H and O-H Bond Activation Across Ta=Ir Multiple Bonds

Author

del Rosal, Iker, Lassalle, Sébastien, Maron, Laurent, Dinoi, Chiara, Thieuleux, Chloé, Camp, Clément, 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)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), 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)-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), Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-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), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Catalyse, Polymérisation, Procédés et Matériaux (CP2M)

Subjects
chemistry.chemical_classification, Steric effects, Double bond, 010405 organic chemistry, Hydrogen bond, 010402 general chemistry, 01 natural sciences, Oxidative addition, Multiple bonds, 0104 chemical sciences, Catalysis, Inorganic Chemistry, Crystallography, chemistry, [CHIM]Chemical Sciences, Bimetallic strip
Abstract

International audience; A rare heterobimetallic oxidative addition of X-H (X = C, O) bonds is reported. DFT suggests that steric constraints around the bimetallic core play a critical role to synergistically activate C-H bonds across the two metals and thus explains the exceptional H/D exchange catalytic activity of unhindered surface organometallic Ta/Ir species observed experimentally.

Published
2020

11. Hydrogen isotope exchange catalyzed by Ru nanocatalysts: labelling of complex molecules containing N-heterocycles and reaction mechanism insights

Author

Pfeifer, Viktor, Certiat, Marie, Bouzouita, Donia, Palazzolo, Alberto, Garcia‐Argote, Sébastien, Marcon, Elodie, Buisson, David‐Alexandre, Lesot, Philippe, Maron, Laurent, Chaudret, Bruno, Tricard, Simon, del Rosal, Iker, Poteau, Romuald, Feuillastre, Sophie, Pieters, Grégory, Service de Chimie Bio-Organique et de Marquage (SCBM), Médicaments et Technologies pour la Santé (MTS), Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Paris-Saclay-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Optoélectronique Quantique (LPCNO), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Fédération de recherche « Matière et interactions » (FeRMI), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), HPCs CALcul en MIdiPyrénées (CALMIP-OLYMPE, grant P1415), The Grand Equipement National de Calcul Intensif (GENCI-TGCC, grant 6211), European Project: 675071,H2020,H2020-MSCA-ITN-2015,ISOTOPICS(2016), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-Université Paris-Saclay, Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-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-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), Université Paris-Saclay, Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Université Paris-Saclay, Modélisation Physique et Chimique (LPCNO), 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 National des Sciences Appliquées - Toulouse (INSA Toulouse), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), 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)-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), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), We acknowledge HPCs CALcul en MIdiPyrénées (CALMIP-OLYMPE, grant P1415) and the Grand Equipement National de Calcul Intensif (GENCI-TGCC, grant 6211) for generous allocations of computer time., Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Heterogeneous catalysis, Full Paper, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Imidazoles, [CHIM.CATA]Chemical Sciences/Catalysis, [CHIM.THER]Chemical Sciences/Medicinal Chemistry, Full Papers, nanocatalysis, Deuterium, Tritium, Catalysis, Ruthenium, Heterocyclic Compounds, Deuteration, [CHIM]Chemical Sciences, N-heterocyclic carbenes, C−H Activation, hydrogen isotopic exchange, Isotopic exchange, C-H activation, [CHIM.RADIO]Chemical Sciences/Radiochemistry, Hydrogen
Abstract

Ruthenium nanocatalysis can provide effective deuteration and tritiation of oxazole, imidazole, triazole and carbazole substructures in complex molecules using D2 or T2 gas as isotopic sources. Depending on the substructure considered, this approach does not only represent a significant step forward in practice, with notably higher isotope uptakes, a broader substrate scope and a higher solvent applicability compared to existing procedures, but also the unique way to label important heterocycles using hydrogen isotope exchange. In terms of applications, the high incorporation of deuterium atoms, allows the synthesis of internal standards for LC‐MS quantification. Moreover, the efficacy of the catalyst permits, even under subatmospheric pressure of T2 gas, the preparation of complex radiolabeled drugs owning high molar activities. From a fundamental point of view, a detailed DFT‐based mechanistic study identifying undisclosed key intermediates, allowed a deeper understanding of C−H (and N−H) activation processes occurring at the surface of metallic nanoclusters., Ruthenium nanocatalysis can provide effective deuteration and tritiation of oxazole, imidazole, triazole and carbazole substructures in complex molecules using D2 or T2 gas as isotopic sources. In terms of application, the high incorporation of deuterium atoms allows the synthesis of deuterated internal standards for LC/MS quantification and the efficacy of the catalytic process permits the preparation of complex radiolabelled drugs owning high specific activities by using a subatmospheric pressure of T2 gas.

Published
2020

14. Regioselective hydrosilylation of terminal alkynes using pentamethylcyclopentadienyl iridium(III) metallacycle catalysts

Author

Niedercorn, Francine, Abadie, Marc-Antoine, Trivelli, Xavier, Medina, Florian, Duhal, Nathalie, Kouach, Mostafa, Linden, Bernhard, Genin, Eric, Vandewalle, Maxence, Capet, Frédéric, Roussel, Pascal, del Rosal, Iker, Maron, Laurent, Agbossou-Niedercorn, Francine, Michon, Christophe, Corre, Yann, Werlé, Christophe, Brelot-Karmazin, Lydia, Djukic, Jean-Pierre, Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Strasbourg, Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), laboratoire de synthèses Métallo-Induites (LSMI), Université Louis Pasteur - Strasbourg I-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS), Unité de Glycobiologie Structurale et Fonctionnelle UMR 8576 (UGSF), Institut National de la Recherche Agronomique (INRA)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Impact de l'environnement chimique sur la santé humaine - ULR 4483 (IMPECS), Université de Lille-Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille), Groupe de Recherche sur les formes Injectables et les Technologies Associées - ULR 7365 (GRITA), European Gravitational Observatory ( EGO ), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), 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)-Institut National Polytechnique (Toulouse) (Toulouse INP), 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 Recherche sur la Fusion par confinement Magnétique (IRFM), Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Unité de Glycobiologie Structurale et Fonctionnelle - UMR 8576 (UGSF), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Institut National de la Recherche Agronomique (INRA), Impact de l'environnement chimique sur la santé humaine (IMPECS), Centre Hospitalier Régional Universitaire [Lille] (CHRU Lille)-Université de Lille, Groupe de Recherche sur les formes Injectables et les Technologies Associées (GRITA)-EA 7365 (GRITA), Unité de Catalyse et de Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Ecole Centrale de Lille-Ecole Nationale Supérieure de Chimie de Lille (ENSCL)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université Fédérale Toulouse Midi-Pyrénées-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)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS), and Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Reaction conditions, Steric effects, 010405 organic chemistry, Hydrosilylation, Process Chemistry and Technology, chemistry.chemical_element, Regioselectivity, Metallacycle, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Organic chemistry, [CHIM]Chemical Sciences, Iridium, Physical and Theoretical Chemistry, Triethylsilane, ComputingMilieux_MISCELLANEOUS
Abstract

Pentamethylcyclopentadienyl iridium(III) metallacycles catalyse the hydrosilylation of alkynes using triethylsilane and no additive. The reactions proceed rapidly and efficiently at low catalyst loadings and under mild reaction conditions. If catalyses starting from terminal alkynes lead selectively to (Z)-alkenylsilanes in high yields, reactions are less efficient and selective starting from internal alkynes due to steric hindrance and the possible formation of isoquinolinium salts. Mass spectrometry highlights up to two consecutive 1,2-insertions of alkynes could take place into the catalyst iridium-carbon bond.

Published
2016

16. A binuclear guanidinate yttrium carbyne complex: unique reactivity toward unsaturated C-N, C-O and C-S bonds.

Author

Jiang W, Kong F, Del Rosal I, Li M, Wang K, Maron L, and Zhang L

Abstract

A guanidinato-stabilized binuclear yttrium carbyne complex [(PhCH 2 ) 2 NC(NC 6 H 3 i Pr 2 -2,6) 2 ] 2 Y 2 (μ 2 -Me)(AlMe 3 ) 2 (μ 4 -CH) (1) was synthesized via C-H bond activation and its versatile reactivities were investigated. Complex 1 underwent σ-bond metathesis with PhSSPh and nucleophilic addition with PhCN to form the corresponding yttrium thiolate complex 3 and aza-allyl complex 4 respectively. Additionally, the rare yttrium carbide complex 5 was also prepared by treatment of complex 1 with S 8 . Interestingly, in the reaction with PhNCS, the C[double bond, length as m-dash]S double bond was cleaved, followed by C-H bond activation to give the yttrium sulfide complex 7 with a ketenimine dianion ligand. Unexpectedly, the reaction of complex 1 with CO (1 atm) resulted in deoxygenative coupling of CO, to afford mono- or dioxo-yttrium complexes at different temperatures. The mechanism of the possible formation processes of complexes 3 and 9 was elucidated by DFT calculations., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

Published
2023
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18. Isolation of C1 through C4 derivatives from CO using heteroleptic uranium(iii) metallocene aryloxide complexes.

Author

Ward RJ, Del Rosal I, Kelley SP, Maron L, and Walensky JR

Abstract

The conversion of C1 feedstock molecules such as CO into commodity chemicals is a desirable, but challenging, endeavour. When the U(iii) complex, [(C 5 Me 5 ) 2 U(O-2,6- t Bu 2 -4-MeC 6 H 2 )], is exposed to 1 atm of CO, only coordination is observed by IR spectroscopy as well as X-ray crystallography, unveiling a rare structurally characterized f element carbonyl. However, using [(C 5 Me 5 ) 2 (MesO)U (THF)], Mes = 2,4,6-Me 3 C 6 H 2 , reaction with CO forms the bridging ethynediolate species, [{(C 5 Me 5 ) 2 (MesO)U} 2 (μ 2 -OCCO)]. While ethynediolate complexes are known, their reactivity has not been reported in much detail to afford further functionalization. For example, addition of more CO to the ethynediolate complex with heating forms a ketene carboxylate, [{(C 5 Me 5 ) 2 (MesO)U} 2 ( μ 2 : κ 2 : η 1 -C 3 O 3 )], which can be further reacted with CO 2 to yield a ketene dicarboxylate complex, [{(C 5 Me 5 ) 2 (MesO)U} 2 ( μ 2 : κ 2 : κ 2 -C 4 O 5 )]. Since the ethynediolate showed reactivity with more CO, we explored its reactivity further. A [2 + 2] cycloaddition is observed with diphenylketene to yield [{(C 5 Me 5 ) 2 U} 2 (OC(CPh 2 )C([double bond, length as m-dash]O)CO)] with concomitant formation of [(C 5 Me 5 ) 2 U(OMes) 2 ]. Surprisingly, reaction with SO 2 shows rare S-O bond cleavage to yield the unusual [(O 2 CC(O)(SO)] 2- bridging ligand between two U(iv) centres. All complexes have been characterized using spectroscopic and structural methods, and the reaction of the ethynediolate with CO to form the ketene carboxylate has been investigated computationally as well as the reaction with SO 2 ., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Published
2023
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19. A versatile strategy for the formation of hydride-bridged actinide-iridium multimetallics.

Author

Ye CZ, Del Rosal I, Boreen MA, Ouellette ET, Russo DR, Maron L, Arnold J, and Camp C

Abstract

Reaction of the potassium pentamethylcyclopentadienyl iridate tris-hydride K[IrCp*H 3 ] with UCl 4 and ThCl 4 (DME) 2 led to the complete replacement of the halide ligands to generate multimetallic complexes U{(μ-H) 3 IrCp*} 4 (1) and Th{[(μ-H 2 )(H)IrCp*] 2 [(μ-H) 3 IrCp*] 2 } (2), respectively. These analogues feature a significant discrepancy in hydride bonding modes; 1 contains twelve bridging hydrides while 2 contains ten bridging hydrides and two terminal, Ir-bound hydrides. Use of a U(iii) starting material, UI 3 (1,4-dioxane) 1.5 , resulted in the octanuclear complex {U[(μ 2 -H 3 )IrCp*] 2 [(μ 3 -H 2 )IrCp*]} 2 (3). Computational studies indicate significant bonding character between U/Th and Ir in 1 and 2, with f-orbital involvement in the singly-occupied molecular orbitals of the uranium species 1. In addition, these studies attribute the variation in hydride bonding between 1 and 2 to differences in dispersion effects., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Published
2022
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20. Divergent uranium- versus phosphorus-based reduction of Me 3 SiN 3 with steric modification of phosphido ligands.

Author

Ward RJ, Rungthanaphatsophon P, Del Rosal I, Kelley SP, Maron L, and Walensky JR

Abstract

We describe an example of a two-electron metal- and ligand-based reduction of Me 3 SiN 3 using uranium(iv) complexes with varying steric properties. Reaction of (C 5 Me 5 ) 2 U(CH 3 )[P(SiMe 3 )(Ph)] with Me 3 SiN 3 produces the imidophosphorane complex, (C 5 Me 5 ) 2 U(CH 3 )[N[double bond, length as m-dash]P(SiMe 3 ) 2 (Ph)] through oxidation of phosphorus. However, a similar reaction with a more sterically encumbering phosphido ligand, (C 5 Me 5 ) 2 U(CH 3 )[P(SiMe 3 )(Mes)] forms the U(iv) complex, (C 5 Me 5 ) 2 U[ κ 2 -( N , N )-N(SiMe 3 )P(Mes)N(SiMe 3 )]. In probing the mechanism of this reaction, a U(vi) bis(imido) complex, (C 5 Me 5 ) 2 U([double bond, length as m-dash]NSiMe 3 ){[double bond, length as m-dash]N[P(SiMe 3 )(Mes)]} was isolated. DFT calculations show an intramolecular reductive cycloaddition reaction leads to the formation of the U(iv) bis(amido)phosphane from the U(vi) bis(imido) complex. This is a rare example of the isolation of a reaction intermediate in f element chemistry., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Published
2020
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