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芳基二锂镍茂的金属转移反应:以金属茂作为二烯配体的异双金属配合物的合成。

Transmetalation Reactions of Aromatic Dilithionickelole: Synthesis of Heterobimetallic Complexes Featuring Metalloles as Diene Ligands.

作者信息

Huang Zhe, Zheng Yu, Zhong Mingdong

机构信息

College of Chemistry, Peking University, Beijing, 100871, China.

Tianjin Key Laboratory of Structure and Performance for Functional Molecules College of Chemistry, Tianjin Normal University, Tianjin, 300387, China.

出版信息

Chemistry. 2021 Nov 17;27(64):15967-15972. doi: 10.1002/chem.202102037. Epub 2021 Oct 13.

Abstract

The aromatic metallole dianions are important metallaaromatic compounds because of their various reactivities and extensive synthetic applications. Herein we report the reactions of dilithionickelole with MgCl , EtAlCl , CpScCl , CpLuCl and Pt(COD)Cl (COD=1,5-cyclooctadiene) affording a series of Ni/M heterobimetallic complexes of the general formula (η -C R M)Ni(COD), in which the metalloles act as diene ligands, as suggested by single-crystal X-ray, NMR and theoretical analyses. In these reactions, two electrons of the nickelole dianion transferred to Ni, representing different reactivity compared with main-group metallole dianions.

摘要

芳香金属环戊二烯二价阴离子是重要的金属芳香化合物,因其具有多种反应活性和广泛的合成应用。在此,我们报道了二锂代镍茂与MgCl₂、EtAlCl₂、CpScCl₂、CpLuCl₂和Pt(COD)Cl₂(COD = 1,5 - 环辛二烯)的反应,得到了一系列通式为(η⁵ - C₅R₅M)Ni(COD)的Ni/M异核双金属配合物,单晶X射线、核磁共振和理论分析表明,其中的金属环戊二烯作为二烯配体。在这些反应中,镍茂二价阴离子的两个电子转移到了镍上,这表明其与主族金属环戊二烯二价阴离子具有不同的反应活性。

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