Tuning σ-Holes: Charge Redistribution in the Heavy (Group 14) Analogues of Simple and Mixed Halomethanes Can Impose Strong Propensities for Halogen Bonding

Authors

Kelling J. Donald, University of RichmondFollow
Bernard K. Wittmaack
Chad Crigger

DOI

10.1021/jp102856v

Abstract

Halogen bonding between halide sites (in substituted organic molecules or inorganic halides) and Lewis bases is a rapidly progressing area of exploration. Investigations of this phenomenon have improved our understanding of weak intermolecular interactions and suggested new possibilities in supramolecular chemistry and crystal engineering. The capacity for halogen bonding is investigated at the MP2(full) level of theory for 100 compounds, including all 80 MH₄-_nX_n systems (M = C, Si, Ge, Sn, and Pb; X = F, Cl, Br, and I). The charge redistribution in these molecules and the (in)stability of the σ-hole at X as a function of M and n are catalogued and examined. For the mixed MH₃-_mF_mI compounds, we identify a complicated dependence of the relative halogen bond strengths on M and m. For m = 0, for example, the H₃C-I----NH₃ halogen bond is 6.6 times stronger than the H₃Pb-I----NH₃ bond. When m = 3, however, the F₃Pb-I----NH₃ bond is shorter and ∼1.6 times stronger than the F₃C-I----NH3 bond. This substituent-induced reversal in the relative strengths of halogen bond energies is explained.

Document Type

Article

Publication Date

2010

Publisher Statement

Copyright © 2010 American Chemical Society. This article first appeared in Journal of Physical Chemistry 114:26 (2010), 7213-7222.

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Recommended Citation

Donald, Keilling J., Bernard K. Wittmaack, and Chad Crigger. "Tuning σ-Holes: Charge Redistribution in the Heavy (Group 14) Analogues of Simple and Mixed Halomethanes Can Impose Strong Propensities for Halogen Bonding." Journal of Physical Chemistry 114, no. 26 (2010): 7213-7222. doi:10.1021/jp102856v.