Revisiting the effect of f‐functions in predicting the right reaction mechanism for hypervalent iodine reagents

Release time:2021-07-02

Impact Factor:2.976

DOI number:10.1002/jcc.26469

Journal:Journal of Computational Chemistry

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, CF3, etc.) bond cleavage and formation, for example, 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.

Co-author:Huakang Zhou, Penggang Yin

First Author:Tian‐Yu Sun

Indexed by:Journal paper

Correspondence Author:Kai Chen*, Tingting You*, Xiao Wang*

Discipline:Natural Science

First-Level Discipline:Chemistry

Document Type:J

Volume:42

Issue:7

Page Number:470-474

Translation or Not:no

Date of Publication:2021-05-15

Included Journals:SCI

Links to published journals:https://onlinelibrary.wiley.com/doi/abs/10.1002/jcc.26469