1. Unusual selective reactivity of the rare-earth metal complexes bearing a ligand with multiple functionalities
- Author
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Dongjing Hong, Thayalan Rajeshkumar, Shan Zhu, Zeming Huang, Shuangliu Zhou, Xiancui Zhu, Laurent Maron, Shaowu Wang, Anhui Normal University, 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), and Anhui Polytechnic University
- Subjects
indole ,Fischer-type carbene ,rare-earth metal complexes ,[CHIM]Chemical Sciences ,dianionic 3-iminoindolyl ,General Chemistry ,N-heterocyclic carbene ,1-migratory insertion - Abstract
International audience; Ligands play a key role in controlling activity of organometallic complexes so that development of new ligands to overcome the challenge is the main topic of modern chemistry. The first example of 1,1-hydride migratory insertion and intramolecular redox reaction has been realized in this work by applying a new ligand in rare-earth metal chemistry. The novel rare-earth metal complexes LMesRECH2TMS(THF) (RE = Y (1a), Dy (1b), Er (1c), Yb (1d), LMes = 1-(3-(2,6-iPr2C6H3N=CH)C8H4N)-CH2CH2-3-(2-CH2—4,6-Me2C6H2)-(N(CH)2NC), THF = tetrahydrofuran) bearing a ligand with imino, indolyl, NHC (N-heterocyclic carbene) multiple functionalities were synthesized and characterized. Treatment of complexes 1 with silanes (PhSiH3 or PhSiH2Me or PhSiD3) selectively produced the unprecedented 1,1-hydride (or deuterated H) migratory insertion of the indolyl moiety of the novel unsymmetrical dinuclear rare-earth metal complexes 2. The complex 2a reacts with Ph2C-O to give the selective C-O double bond insertion to the RE-Co-methylene-Mes bond product 3a which further reacts with another Ph2C-O (or DMAP, 4-N, N-dimethylaminopyridine) affording the novel μ-η2:η3-dianionic 3-iminoindolyl dinuclear rare-earth metal complex 4a. The latter is formed through an unusual intramolecular redox reaction (through electron migration from the 2-carbanion of the indolyl ring to the imino motif) resulting in the re-aromatization of the indolyl ring.
- Published
- 2022
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