期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 26, 期 17, 页码 3843-3861出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201905273
关键词
bond energy; density functional calculations; halogen bonding; iodine; Lewis acids
Halogen-bond donors (halogen-based Lewis acids) have now found various applications in diverse fields of chemistry. The goal of this study was to identify a parameter obtainable from a single DFT calculation that reliably describes halogen-bonding strength (Lewis acidity). First, several DFT methods were benchmarked against the CCSD(T) CBS binding data of complexes of 17 carbon-based halogen-bond donors with chloride and ammonia as representative Lewis bases, which revealed M05-2X with a partially augmented def2-TZVP(D) basis set as the best model chemistry. The best single parameter to predict halogen-bonding strengths was the static sigma-hole depth, but it still provided inaccurate predictions for a series of compounds. Thus, a more reliable parameter, omega(sigma*), has been developed through the linear combination of the sigma-hole depth and the sigma*(C-I) energy, which was further validated against neutral, cationic, halogen- and nitrogen-based halogen-bond donors with very good performance.
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