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Revisiting the effect of f ‐functions in predicting the right reaction mechanism for hypervalent iodine reagents
Author(s) -
Sun TianYu,
Chen Kai,
Zhou Huakang,
You Tingting,
Yin Penggang,
Wang Xiao
Publication year - 2021
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26469
Subject(s) - hypervalent molecule , reagent , chemistry , iodine , computational chemistry , reaction mechanism , mechanism (biology) , twist , combinatorial chemistry , stereochemistry , organic chemistry , mathematics , catalysis , physics , quantum mechanics , geometry
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.