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添加配体对[Ni(COD)(dppf)]与卤代烃反应的影响：卤化物的夺取可能是可逆的。

The Effect of Added Ligands on the Reactions of [Ni(COD)(dppf)] with Alkyl Halides: Halide Abstraction May Be Reversible.

作者信息

Greaves Megan E, Ronson Thomas O, Maseras Feliu, Nelson David J

机构信息

WestCHEM Department of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland.

Chemical Development, Pharmaceutical Technology and Development, Operations, AstraZeneca, Macclesfield SK10 2NA, U.K.

出版信息

Organometallics. 2021 Jun 28;40(12):1997-2007. doi: 10.1021/acs.organomet.1c00280. Epub 2021 Jun 16.

DOI:10.1021/acs.organomet.1c00280
PMID:34295014
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8288641/
Abstract

The reactions of dppf-nickel(0) with alkyl halides proceed via three-coordinate nickel(0) intermediates of the form [Ni(dppf)(L)]. The effects of the identity of the added ligand (L) on catalyst speciation and the rates of reactions of [Ni(COD)(dppf)] with alkyl halides have been investigated using kinetic experiments and density functional theory calculations. A series of monodentate ligands have been investigated in attempts to identify trends in reactivity. Sterically bulky and electron-donating ligands are found to decrease the reaction rate. It was found that (i) the halide abstraction step is not always irreversible and the subsequent recombination of a nickel(I) complex with an alkyl halide can have a significant effect on the overall rate of the reaction and (ii) some ligands lead to very stable [Ni(dppf)(L)] species. The yields of prototypical (dppf)nickel-catalyzed Kumada cross-coupling reactions of alkyl halides are significantly improved by the addition of free ligands, which provides another important variable to consider when optimizing nickel-catalyzed reactions of alkyl halides.

摘要

双(二苯基膦基)二茂铁镍(0)与卤代烃的反应通过[Ni(dppf)(L)]形式的三配位镍(0)中间体进行。使用动力学实验和密度泛函理论计算，研究了添加配体(L)的种类对催化剂形态以及[Ni(COD)(dppf)]与卤代烃反应速率的影响。为了确定反应活性趋势，研究了一系列单齿配体。发现空间位阻大的给电子配体会降低反应速率。研究发现：(i) 卤化物夺取步骤并非总是不可逆的，镍(I)配合物与卤代烃随后的重新结合会对反应的总速率产生显著影响；(ii) 一些配体会导致形成非常稳定的[Ni(dppf)(L)]物种。通过添加游离配体，典型的(dppf)镍催化卤代烃库马德交叉偶联反应的产率得到显著提高，这为优化镍催化卤代烃反应时提供了另一个需要考虑的重要变量。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3b1f/8288641/68b95dd9f70a/om1c00280_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3b1f/8288641/ab5b4447261d/om1c00280_0005.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3b1f/8288641/594ba790a532/om1c00280_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3b1f/8288641/95ed46e59d4e/om1c00280_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3b1f/8288641/d8a3cc14b245/om1c00280_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3b1f/8288641/a9bf4dadd05a/om1c00280_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3b1f/8288641/68b95dd9f70a/om1c00280_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3b1f/8288641/ab5b4447261d/om1c00280_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3b1f/8288641/712c2c6f6a15/om1c00280_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3b1f/8288641/594ba790a532/om1c00280_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3b1f/8288641/95ed46e59d4e/om1c00280_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3b1f/8288641/d8a3cc14b245/om1c00280_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3b1f/8288641/a9bf4dadd05a/om1c00280_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/3b1f/8288641/68b95dd9f70a/om1c00280_0004.jpg

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