Understanding titanium-catalysed radical-radical reactions: a DFT study unravels the complex kinetics of ketone-nitrile couplings.
Understanding titanium-catalysed radical-radical reactions: a DFT study unravels the complex kinetics of ketone-nitrile couplings.
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DOI：
10.1039/c8dt00643a
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发表时间：
2018-04
影响因子：
4
通讯作者：
Jan Streuff;D. Himmel;S. Younas
中科院分区：
文献类型：
--
作者：
Jan Streuff;D. Himmel;S. Younas
报道了钛催化还原性自由基-自由基偶联反应的计算研究。结果符合从早期的实验研究的结论，并使以前观察到的复杂的反应动力学的进一步解释。此外，在钛（III）催化反应的中性和阳离子反应途径之间的相互作用进行了研究的第一次。结果表明，盐酸盐添加剂和反应副产物在各自的平衡中起重要作用。一个完整的反应配置文件组装和计算的活化势垒被发现是在合理的协议与实验。所得结论对低价钛催化领域及相关催化自由基-自由基偶联反应的理解具有重要意义。
The computational investigation of a titanium-catalysed reductive radical-radical coupling is reported. The results match the conclusions from an earlier experimental study and enable a further interpretation of the previously observed complex reaction kinetics. Furthermore, the interplay between neutral and cationic reaction pathways in titanium(iii)-catalysed reactions is investigated for the first time. The results show that hydrochloride additives and reaction byproducts play an important role in the respective equilibria. A full reaction profile is assembled and the computed activation barrier is found to be in reasonable agreement with the experiment. The conclusions are of fundamental importance to the field of low-valent titanium catalysis and the understanding of related catalytic radical-radical coupling reactions.