Academic Journal
Experimental and Theoretical Insights into the Electronic Properties of Anionic N-Heterocyclic Dicarbenes through the Rational Synthesis of Their Transition Metal Complexes
| العنوان: | Experimental and Theoretical Insights into the Electronic Properties of Anionic N-Heterocyclic Dicarbenes through the Rational Synthesis of Their Transition Metal Complexes |
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| المؤلفون: | Grineva, Alina, A, Filippov, Oleg, A, Canac, Yves, Sortais, Jean-Baptiste, Nefedov, Sergei, E, Lugan, Noël, César, Vincent, Valyaev, Dmitry, A. |
| المساهمون: | 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 - CNRS Chimie (INC-CNRS)-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), N. S. Kurnakov Institute of General and Inorganic Chemistry (IGIC), Russian Academy of Sciences Moscow (RAS), A. N. Nesmeyanov Institute of Organoelement Compounds (INEOS), Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry (IBCh RAS), Institut universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Centre National de la Recherche Scientifique (CNRS), Institut Universitaire de France (IUF), French embassy in Moscow, Ministry of Science and Higher Education of the Russian Federation |
| المصدر: | ISSN: 0020-1669. |
| بيانات النشر: | HAL CCSD American Chemical Society |
| سنة النشر: | 2021 |
| المجموعة: | Université Toulouse III - Paul Sabatier: HAL-UPS |
| مصطلحات موضوعية: | Carbene compounds, Reaction products, Ligands, Bimetals, Transition metals, [CHIM.COOR]Chemical Sciences/Coordination chemistry |
| الوصف: | International audience ; The lithiation of the NHC ligand backbone in Cp(CO)2Mn(IMes) followed by transmetalation on the C4 carbenic position with Cp(CO)2FeI led to the heterobimetallic complex Cp(CO)2Mn(μ-dIMes)Fe(CO)2Cp bearing the anionic ditopic imidazol-2,4-diylidene dIMes ligand. Subsequent treatment of the later with TfOH induced a selective decoordination of the [Cp(CO)2Mn] fragment to form the cationic abnormal NHC complex [Cp(CO)2Fe(aIMes)](OTf), which was further derivatized to the bis(iron) dIMes complex [Cp(CO)2Fe(μ-dIMes)Fe(CO)2Cp](OTf) by reaction with tAmOK and Cp(CO)2FeI. The effect of the metalation at the C4 or C2 position on the imidazole ring on the electronic donation properties of the associated C2 and C4 carbenic centers in the dIMes ligand was quantified through systematic experimental and theoretical studies of IMes, aIMes, and dIMes complexes. The evaluation of the catalytic activity of the series of cationic Fe(II) complexes based on IMes, aIMes, and dIMes ligands in a benchmark ketone hydrosilylation showed the superiority of the bimetallic derivative. |
| نوع الوثيقة: | article in journal/newspaper |
| اللغة: | English |
| Relation: | hal-03200528; https://hal.science/hal-03200528; https://hal.science/hal-03200528/document; https://hal.science/hal-03200528/file/Revised_manuscript-1.pdf |
| DOI: | 10.1021/acs.inorgchem.1c00073 |
| الاتاحة: | https://hal.science/hal-03200528 https://hal.science/hal-03200528/document https://hal.science/hal-03200528/file/Revised_manuscript-1.pdf https://doi.org/10.1021/acs.inorgchem.1c00073 |
| Rights: | info:eu-repo/semantics/OpenAccess |
| رقم الانضمام: | edsbas.E55367EE |
| قاعدة البيانات: | BASE |
| DOI: | 10.1021/acs.inorgchem.1c00073 |
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