Thermodynamics of Halogen Bonding in Solution: Substituent, Structural, and Solvent Effects

A detailed study of the thermodynamics of the halogen-bonding interaction in organic solution is presented. 19F NMR titrations are used to determine association constants for the interactions of a variety of Lewis bases with fluorinated iodoalkanes and iodoarenes. Linear free energy relationships fo...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2010-02, Vol.132 (5), p.1646-1653
Main Authors: Sarwar, Mohammed G, Dragisic, Bojan, Salsberg, Lee J, Gouliaras, Christina, Taylor, Mark S
Format: Article
Language:English
Subjects:
Halogens - chemistry
Models, Molecular
Molecular Structure
Solutions - chemistry
Solvents - chemistry
Thermodynamics
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Summary:A detailed study of the thermodynamics of the halogen-bonding interaction in organic solution is presented. 19F NMR titrations are used to determine association constants for the interactions of a variety of Lewis bases with fluorinated iodoalkanes and iodoarenes. Linear free energy relationships for the halogen bond donor ability of substituted iodoperfluoroarenes XC6F4I are described, demonstrating that both substituent constants (σ) and calculated molecular electrostatic potential surfaces are useful for constructing such relationships. An electrostatic model is, however, limited in its ability to provide correlation with a more comprehensive data set in which both halogen bond donor and acceptor abilities are varied: the ability of computationally derived binding energies to accurately model such data is elucidated. Solvent effects also reveal limitations of a purely electrostatic depiction of halogen bonding and point to important differences between halogen bonding and hydrogen bonding.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja9086352