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The competition of Y⋯o and X⋯n halogen bonds to enhance the group V σ‐hole interaction in the NCY⋯o PH 3 ⋯ NCX and O PH 3 ⋯ NCX⋯NCY ( X, Y F, Cl , and Br ) complexes
Author(s) -
Li Wei,
Zeng Yanli,
Li Xiaoyan,
Sun Zheng,
Meng Lingpeng
Publication year - 2015
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.23922
Subject(s) - halogen , group (periodic table) , chemistry , competition (biology) , crystallography , organic chemistry , biology , ecology , alkyl
The positive electrostatic potentials (ESP) outside the σ‐hole along the extension of OP bond in OPH 3 and the negative ESP outside the nitrogen atom along the extension of the CN bond in NCX could form the Group V σ‐hole interaction OPH 3 ⋯NCX. In this work, the complexes NCY⋯OPH 3 ⋯NCX and OPH 3 ⋯NCX⋯NCY (X, YF, Cl, Br) were designed to investigate the enhancing effects of Y⋯O and X⋯N halogen bonds on the P⋯N Group V σ‐hole interaction. With the addition of Y⋯O halogen bond, the V S, max values outside the σ‐hole region of OPH 3 becomes increasingly positive resulting in a stronger and more polarizable P⋯N interaction. With the addition of X⋯N halogen bond, the V S, min values outside the nitrogen atom of NCX becomes increasingly negative, also resulting in a stronger and more polarizable P⋯N interaction. The Y⋯O halogen bonds affect the σ‐hole region (decreased density region) outside the phosphorus atom more than the P⋯N internuclear region (increased density region outside the nitrogen atom), while it is contrary for the X⋯N halogen bonds. © 2015 Wiley Periodicals, Inc.