Unusual selective reactivity of the rare-earth metal complexes bearing a ligand with multiple functionalities

作     者：Dongjing Hong Thayalan Rajeshkumar Shan Zhu Zeming Huang Shuangliu Zhou Xiancui Zhu Laurent Maron Shaowu Wang 

作者机构：Key Laboratory of Functional Molecular SolidsMinistry of EducationAnhui Laboratory of Molecule-Based MaterialsCollege of Chemistry and Materials ScienceAnhui Normal UniversityWuhu 241000China Anhui Laboratory of Clean Catalytic EngineeringAnhui Laboratory of Functional Coordinated Complexes for Materials Chemistiry and ApplicationCollege of Chemical and Environmental EngineeringAnhui Polytechnic UniversityWuhu 241000China LPCNOCNRS&INSAUniversite Paul Sabatier 135 Avenue de Rangueil31077 ToulouseFrance 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2023年第66卷第1期

页      面：117-126页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 070304[理学-物理化学(含∶化学物理)] 08[工学] 0817[工学-化学工程与技术] 0703[理学-化学] 

基　　金：supported by the National Natural Science Foundation of China(22031001,21871004,21861162009,22171004) the grants from the Education Department of Anhui Province(GXXT-2021-052) 

主　　题：rare-earth metal complexes indole N-heterocyclic carbene Fischer-type carbene 1 1-migratory insertion dianionic 3-iminoindolyl 

摘      要：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 *** 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 *** novel rare-earth metal complexes L^(Mes)RECH2TMS(THF)(RE=Y(1a),Dy(1b),Er(1c),Yb(1d),L^(Mes)=1-(3-(2,6-iPr_(2)C_(6)H_(3)N=CH)C8H4N)-CH_(2)CH_(2)-3-(2-CH2–4,6-Me_(2)C_(6)H_(2))-(N(CH)_(2)NC),THF=tetrahydrofuran)bearing a ligand with imino,indolyl,NHC(N-heterocyclic carbene)multiple functionalities were synthesized and *** of complexes 1 with silanes(PhSiH3or 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 *** complex 2a reacts with Ph_(2)C=O to give the selective C=O double bond insertion to the RE–Co-methylene-Mesbond product 3a which further reacts with another Ph_(2)C=O(or DMAP,4-N,N-dimethylaminopyridine)affording the novelμ-η^(2):η^(3)-dianionic 3-iminoindolyl dinuclear rare-earth metal complex *** 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.