[Rh2(phesp)2]：在碳烯 C-H 插入反应中调节位点选择性的更笨重的[Rh2(esp)2]类似物

IF 3.8 3区化学 Q2 CHEMISTRY, PHYSICAL

ChemCatChem Pub Date : 2024-09-06 DOI:10.1002/cctc.202400874

Agnès Labande, Illia Ruzhylo, Anna Vorozhbian, Sandrine Vincendeau, Tanguy Saget, Sonia Mallet-Ladeira, Philippe Dauban, Eric Manoury

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引用次数: 0

摘要

[Rh2(phesp)2]是一种新的二铑(II)配合物，带有笨重的双齿双羧酸配体，由市售化合物通过两个步骤制备而成。它的 X 射线结构显示出与众不同的特征，即在二铑(II)核心周围有强烈的畸变，重要的扭转角高达 9.0°。在碳烯烃 C-H 插入反应中，它作为著名的[Rh2(esp)2]复合物的膨大版催化剂进行了评估。事实证明，[Rh2(phesp)2]与[Rh2(esp)2]具有同样的活性，而且在与供体-受体和受体-受体重氮化合物的分子内和分子间反应中，其选择性介于[Rh2(esp)2]和笨重的[Rh2(tpa)4]之间。

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[Rh2(phesp)2]: a Bulkier [Rh2(esp)2] Analog to Tune the Site‐Selectivity in Carbene C–H Insertion Reactions

[Rh2(phesp)2], a new dirhodium(II) complex bearing a bulky bidentate bis‐carboxylate ligand, has been prepared in two steps from commercially available compounds. Its X‐ray structure revealed distinctive features with a strong distortion around the dirhodium(II) core, illustrated by important torsion angles of up to 9.0°. It has been evaluated as catalyst as a bulky version of the prominent [Rh2(esp)2] complex in carbene C–H insertion reactions. [Rh2(phesp)2] proved as active as [Rh2(esp)2], and showed an intermediate selectivity between [Rh2(esp)2] and bulky [Rh2(tpa)4] in both intra‐ and intermolecular reactions with donor‐acceptor and acceptor‐acceptor diazo compounds, comprising challenging C(sp3)–H insertion into pentane.

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来源期刊

ChemCatChem 化学-物理化学

CiteScore

8.10

自引率

4.40%

发文量

511

审稿时长

1.3 months

期刊介绍： With an impact factor of 4.495 (2018), ChemCatChem is one of the premier journals in the field of catalysis. The journal provides primary research papers and critical secondary information on heterogeneous, homogeneous and bio- and nanocatalysis. The journal is well placed to strengthen cross-communication within between these communities. Its authors and readers come from academia, the chemical industry, and government laboratories across the world. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies, and is supported by the German Catalysis Society.