Revisiting the effect of <scp><i>f</i></scp>‐functions in predicting the right reaction mechanism for hypervalent iodine reagents
Tian‐Yu Sun, Kai Chen, Huakang Zhou, Tingting You, Penggang Yin, Xiao Wang
Abstract
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 IX (X = O, OH, CF 3 , 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 . Our findings may be helpful for theoretical chemists to appropriately study the reaction mechanism of hypervalent iodine reagents.