Kinetic Analysis Uncovers Hidden Autocatalysis and Inhibition Pathways in Titanium(III)-Catalyzed Ketone-Nitrile Couplings,ACS Catalysis

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Kinetic Analysis Uncovers Hidden Autocatalysis and Inhibition Pathways in Titanium(III)-Catalyzed Ketone-Nitrile Couplings
ACS Catalysis ( IF 11.3 ) Pub Date : 2021-08-31 , DOI: 10.1021/acscatal.1c02870
Sara L. Younas ₁ , Jan Streuff _{1,

2}

Affiliation

Through kinetic analysis, we demonstrate that the formation of catalyst and substrate reservoirs plays a crucial role in the titanium(III)-catalyzed ketone-nitrile coupling reaction. Together with the insight from previous studies, a kinetic model is assembled that reflects the observed influence of ZnCl₂ and Et₃N byproducts as well as the hydrochloride additive, which is employed frequently in titanium(III) catalysis. We further propose for the Cp₂TiCl₂-catalyzed reaction that the acceleration phase of the reaction originates from a hidden autocatalytic cycle, which leads to a change in the rate-determining step over the course of the reaction.

中文翻译：

动力学分析揭示了钛 (III) 催化的酮-腈偶联物中隐藏的自催化和抑制途径

通过动力学分析，我们证明催化剂和底物储层的形成在钛 (III) 催化的酮腈偶联反应中起着至关重要的作用。结合先前研究的见解，组装了一个动力学模型，该模型反映了观察到的 ZnCl ₂和 Et ₃ N 副产物以及常用于钛 (III) 催化的盐酸盐添加剂的影响。我们进一步建议，对于 Cp ₂ TiCl ₂催化的反应，反应的加速阶段源于隐藏的自催化循环，这导致反应过程中的速率决定步骤发生变化。

更新日期：2021-09-17

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