Towards understanding the kinetic behaviour and limitations in photo-induced copper(i) catalyzed azide-alkyne cycloaddition (CuAAC) reactions.
Towards understanding the kinetic behaviour and limitations in photo-induced copper(i) catalyzed azide-alkyne cycloaddition (CuAAC) reactions.
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DOI：
10.1039/c6cp04950h
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发表时间：
2016-09-14
期刊：
影响因子：
--
通讯作者：
Kloxin CJ
中科院分区：
文献类型：
--
作者：
El-Zaatari BM;Shete AU;Adzima BJ;Kloxin CJ
使用实时傅里叶变换红外光谱 (FTIR) 在溶剂型单官能团和纯聚合物网络形成体系上详细研究了光诱导铜 (I) 催化叠氮化物-炔烃环加成 (CuAAC) 反应的动力学行为。溶剂型体系的结果显示，铜和光引发剂浓度达到接近一级动力学，达到阈值时动力学切换至零级。这种动力学转变表明光-CuAAC 反应不易受到副反应的影响，例如反应早期阶段的铜歧化、铜(I) 还原和自由基终止。总反应速率和转化率高度依赖于光引发剂和铜(II) 的初始浓度以及它们的相对比例。当使用与其阈值相比过量的光引发剂时，转化率会降低。有趣的是，反应显示出相对较低强度的诱导期。通过增加光强度和光引发剂浓度来缩短诱导期。在无溶剂聚合物网络形成系统中进一步观察到反应趋势和局限性，表现出类似的铜和光引发剂阈值行为。
The kinetic behaviour of the photo-induced copper(I) catalyzed azide—alkyne cycloaddition (CuAAC) reaction was studied in detail using real-time Fourier Transform Infrared Spectroscopy (FTIR) on both a solvent-based monofunctional and a neat polymer network forming system. The results in the solvent-based system showed near first-order kinetics on copper and photoinitiator concentrations up to a threshold value in which the kinetics switch to zeroth-order. This kinetic shift shows that the photo-CuAAC reaction is not suseptible from side reactions such as copper disproportionation, copper(I) reduction, and radical termination at the early stages of the reaction. The overall reaction rate and conversion is highly dependent on the initial concentrations of photoinitiator and copper(II), as well as their relative ratios. The conversion was decreased when an excess of photoinitiator was utilized compared to its threshold value. Interestingly, the reaction showed an induction period at relatively low intensities. The induction period is decreased by increasing light intensity, and photoinitiator concentration. The reaction trends and limitations were further observed in a solventless polymer network forming system, exhibiting a similar copper and photoinitiator threshold behaviour.
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