A CuI/CuIII prototypical organometallic mechanism for the deactivation of an active pincer-like CuI catalyst in Ullmann-type couplings,Chemical Communications

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A CuI/CuIII prototypical organometallic mechanism for the deactivation of an active pincer-like CuI catalyst in Ullmann-type couplings
Chemical Communications ( IF 4.3 ) Pub Date : 2017-07-13 00:00:00 , DOI: 10.1039/c7cc04491g
Mireia Rovira _{1,

2,

3,

4,

5} , Lucie Jašíková _{6,

7,

8,

9,

10} , Erik Andris _{6,

7,

8,

9,

10} , Ferran Acuña-Parés _{1,

2,

3,

4,

5} , Marta Soler _{1,

2,

3,

4,

5} , Imma Güell _{1,

2,

3,

4,

5} , Ming-Zheng Wang _{1,

2,

3,

4,

5} , Laura Gómez _{1,

2,

3,

4,

5} , Josep M. Luis _{1,

2,

3,

4,

5} , Jana Roithová _{6,

7,

8,

9,

10} , Xavi Ribas _{1,

2,

3,

4,

5}

Affiliation

Unraveling the mechanistic details of copper-catalyzed arylation of nucleophiles (Ullmann-type couplings) is a very challenging task. It is a matter of intense debate whether it is a radical-based process or an organometallic redox-based process. The ancillary ligand choice in Ullmann-type couplings plays a key role in such transformations and can strongly influence the catalytic efficiency as well as the mechanism. Here, we show how a predesigned tridentate pincer-like catalyst undergoes a deactivation pathway through a Cu^I/Cu^III prototypical mechanism as demonstrated by helium-tagging infrared photodissociation (IRPD) spectroscopy and DFT studies, lending a strong support to the existence of an aryl–Cu^III species in the Ullmann couplings using this tridentate ligand.

中文翻译：

Cu ^I / Cu ^III原型有机金属机制，用于钝化Ullmann型偶联中的活性钳状Cu ^I催化剂

阐明亲核试剂的铜催化芳基化（Ullmann型偶联）的机理细节是一项非常具有挑战性的任务。无论是基于自由基的过程还是基于有机金属氧化还原的过程，都引起了激烈的争论。乌尔曼型偶联中辅助配体的选择在此类转化中起关键作用，并且可以强烈影响催化效率及其机理。在这里，我们展示了预先设计的三齿钳状催化剂如何通过Cu ^I / Cu ^III原型机制经历失活途径，如氦标记红外光解离（IRPD）光谱法和DFT研究所证明的那样，为存在一种强力支撑提供了有力支持。芳基铜^III 使用该三齿配体的Ullmann偶联中的其他物种。

更新日期：2017-07-22

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