论文标题
重新审查F功能在预测过度碘试剂的正确反应机制中的影响
Revisiting the Effect of f-Functions in Predicting the Right Reaction Mechanism for Hypervalent Iodine Reagents
论文作者
论文摘要
为了了解F功能在预测过度碘试剂的正确反应机制方面的影响，我们采用Ahlrichs基础设置族DEF2-SVP和DEF2-TZVP来重新审视IBX介导的氧化和Togni I的势能表面。我们的结果进一步证明，F功能（在罂粟，dunning或ahlrichs基集系列中）是必不可少的，以预测高价值碘试剂的正确速率定位步骤。 F功能对涉及I-X的过程（X = O，OH，CF $ _3 $等）的过程的预测反应屏障具有重大影响，例如在还原的消除步骤或超价扭曲步骤中。我们还探索了两种高价值的扭曲模式，这些模式解释了IBX和Togni I的F功能的不同影响。我们的发现可能对理论化学家适当研究高价值碘试剂的反应机制可能有所帮助。
To understand the effect of f-functions in predicting the right reaction mechanism for hypervalent iodine reagents, we adopt the Ahlrichs basis set family def2-SVP and def2-TZVP to revisit the potential energy surfaces of IBX-mediated oxidation and Togni I's isomerisation. Our results further prove that f-functions (in either Pople, Dunning, or Ahlrichs basis set series) are indispensable to predict the correct rate-determining step of hypervalent iodine reagents. The f-functions have a significant impact on the predicted reaction barriers for processes involving the I-X (X = O, OH, CF$_3$, etc.) bond cleavage and formation, e.g. in the reductive elimination step or the hypervalent twist step. We furthermore explore two hypervalent twist modes that account for the different influences of f-functions for IBX and Togni I. Our findings may be helpful for theoretical chemists to appropriately study the reaction mechanism of hypervalent iodine reagents.
