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迈向异配位双配位铜配合物

Towards Heteroleptic Dicoordinate Cu Complexes.

作者信息

Kaiser Michelle, Göttlicher Jörg, Vitova Tonya, Hinz Alexander

机构信息

Karlsruher Institut für Technologie, Institut für Anorganische Chemie (AOC), Engesserstrasse 15, 76131, Karlsruhe, Germany.

Karlsruher Institut für Technologie, Institut für Photonenforschung und Synchrotronstrahlung (IPS), Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen, Germany.

出版信息

Chemistry. 2021 May 26;27(30):7998-8002. doi: 10.1002/chem.202100888. Epub 2021 May 2.

DOI:10.1002/chem.202100888
PMID:33834548
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8252544/
Abstract

In this work we detail our efforts to systematically generate stable dicoordinate Cu complexes. Initial experiments via metathesis reactions of a bulky potassium carbazolide (RK) with copper(II) salts indeed yielded a stable product, RCuOTf (1). However, subsequent attempts to grasp systematic synthetic access to complexes of the type RCuX (X=monoanionic ligand) proved difficult as many of the complexes rapidly decomposed in solution. By using triflate-related ligands such as ethyl sulfate and bistriflimide, the additional dicoordinate copper complexes RCuOSO Et (2), [RCu(THF)][Cu(NTf ) ] (3) and RCuNTf (4) could be isolated. Spectroscopic indications corroborate more Cu than Cu character in all RCuX derivatives.

摘要

在这项工作中，我们详细阐述了系统生成稳定双配位铜配合物的努力。通过大位阻咔唑钾（RK）与铜（II）盐的复分解反应进行的初步实验确实得到了一种稳定的产物RCuOTf（1）。然而，随后试图系统合成RCuX类型（X = 单阴离子配体）配合物的尝试证明很困难，因为许多配合物在溶液中迅速分解。通过使用与三氟甲磺酸根相关的配体，如硫酸乙酯和双（三氟甲磺酰）亚胺，可以分离出额外的双配位铜配合物RCuOSO₂Et（2）、[RCu(THF)][Cu(NTf₂)₂]（3）和RCuNTf₂（4）。光谱学迹象证实，在所有RCuX衍生物中，Cu（I）的特征比Cu（II）更多。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5ca/8252544/52ea47692b5a/CHEM-27-7998-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5ca/8252544/bebdee7997c4/CHEM-27-7998-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5ca/8252544/4787430c84d5/CHEM-27-7998-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5ca/8252544/d78946b18fae/CHEM-27-7998-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5ca/8252544/91963968a010/CHEM-27-7998-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5ca/8252544/075923fb9101/CHEM-27-7998-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5ca/8252544/52ea47692b5a/CHEM-27-7998-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5ca/8252544/bebdee7997c4/CHEM-27-7998-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5ca/8252544/4787430c84d5/CHEM-27-7998-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5ca/8252544/d78946b18fae/CHEM-27-7998-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5ca/8252544/91963968a010/CHEM-27-7998-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5ca/8252544/075923fb9101/CHEM-27-7998-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/c5ca/8252544/52ea47692b5a/CHEM-27-7998-g005.jpg

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