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Is There a Single Ideal Parameter for Halogen-Bonding-Based Lewis Acidity?

ABSTRACT: 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 ?-hole depth, but it still provided inaccurate predictions for a series of compounds. Thus, a more reliable parameter, ??* , has been developed through the linear combination of the ?-hole depth and the ?*(C-I) energy, which was further validated against neutral, cationic, halogen- and nitrogen-based halogen-bond donors with very good performance.

SUBMITTER: Engelage E

PROVIDER: S-EPMC7154672 | biostudies-literature | 2020 Mar

REPOSITORIES: biostudies-literature

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Is There a Single Ideal Parameter for Halogen-Bonding-Based Lewis Acidity?

Engelage Elric E Reinhard Dominik D Huber Stefan M SM

Chemistry (Weinheim an der Bergstrasse, Germany) 20200309 17

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 partial ...[more]

PMID: 31943430

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