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

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. Our findings may be helpful for theoretical chemists to appropriately study the reaction mechanism of hypervalent iodine reagents.