Department of Chemistry, Lash Miller Chemical Laboratories, University of Toronto, Toronto, Ontario M5S 3H6, Canada.
J Am Chem Soc. 2010 Feb 10;132(5):1646-53. doi: 10.1021/ja9086352.
A detailed study of the thermodynamics of the halogen-bonding interaction in organic solution is presented. (19)F 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 XC(6)F(4)I are described, demonstrating that both substituent constants (sigma) 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.
本文详细研究了有机溶液中卤键相互作用的热力学。（19）F NMR 滴定法用于测定各种路易斯碱与氟化碘代烷和碘代芳烃相互作用的结合常数。描述了取代的全氟碘代芳烃 XC(6)F(4)I 卤键供体能力的线性自由能关系，表明取代常数（sigma）和计算的分子静电势表面都可用于构建这种关系。然而，静电模型在与更全面的数据集相关联方面存在局限性，其中同时改变了卤键供体和受体的能力：计算得出的结合能准确模拟此类数据的能力得到了阐明。溶剂效应也揭示了纯静电描绘卤键的局限性，并指出了卤键与氢键之间的重要区别。
