Mechanistic Insights into C(sp2 )-C(sp)N Reductive Elimination from Gold(III) Cyanide Complexes.,Angewandte Chemie International Edition

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Mechanistic Insights into C(sp2 )-C(sp)N Reductive Elimination from Gold(III) Cyanide Complexes.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-07-10 , DOI: 10.1002/anie.202005731
Alexandre Genoux ₁ , Jorge A González ₁ , Estíbaliz Merino _{1,

2} , Cristina Nevado ₁

Affiliation

A new family of phosphine‐ligated dicyanoarylgold(III) complexes has been prepared and their reactivity towards reductive elimination has been studied in detail. Both, a highly positive entropy of activation and a primary ^12/13C KIE suggest a late concerted transition state while Hammett analysis and DFT calculations indicate that the process is asynchronous. As a result, a distinct mechanism involving an asynchronous concerted reductive elimination for the overall C(sp²)−C(sp)N bond forming reaction is characterized herein, for the first time, complementing previous studies reported for C(sp³)−C(sp³), C(sp²)−C(sp²), and C(sp³)−C(sp²) bond formation processes taking place on gold(III) species.

中文翻译：

从氰化金（III）络合物还原C（sp2）-C（sp）N的机理研究。

已制备了新的膦连接的二氰基芳基金（III）配合物家族，并已详细研究了它们对还原消除的反应性。激活的高度正熵和主要的^12/13 C KIE都表明后期的过渡过渡态，而Hammett分析和DFT计算表明该过程是异步的。结果，本文首次表征了涉及整个C（sp ²）-C（sp）N键形成反应的异步协同还原消除的独特机制，是对先前报道的C（sp ³）-研究的补充C（sp ³），C（sp ²）-C（sp ²）和C（sp ³）-C（sp ²）在金（III）物种上发生的键形成过程。

更新日期：2020-07-10

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