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arXiv · 2005.09831

Revisiting the Effect of f-Functions in Predicting the Right Reaction Mechanism for Hypervalent Iodine Reagents

Tian-Yu Sun·Kai Chen·Huakang Zhou·Tingting You·Penggang Yin·Xiao Wang
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Abstract

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.

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Tian-Yu Sun, Kai Chen, Huakang Zhou, Tingting You, Penggang Yin, Xiao Wang. 2020-05-20. Revisiting the Effect of f-Functions in Predicting the Right Reaction Mechanism for Hypervalent Iodine Reagents. https://arxiv.org/abs/2005.09831

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