The competition of Y⋯O and X⋯N halogen bonds to enhance the group V σ-hole interaction in the NCY⋯O=PH3 ⋯NCX and O=PH3 ⋯NCX⋯NCY (X, Y=F, Cl, and Br) complexes.
The positive electrostatic potentials (ESP) outside the σ-hole along the extension of OP bond in OPH3 and the negative ESP outside the nitrogen atom along the extension of the CN bond in NCX could form the Group V σ-hole interaction OPH3 ⋯NCX. In this work, the complexes NCY⋯OPH3 ⋯NCX and OPH3 ⋯NCX⋯NCY (X, YF, 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 VS, max values outside the σ-hole region of OPH3 becomes increasingly positive resulting in a stronger and more polarizable P⋯N interaction. With the addition of X⋯N halogen bond, the VS, 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.
Institute of Computational Quantum Chemistry, College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang, 050024, People's Republic of China.
Wei
W
Li
Institute of Computational Quantum Chemistry, College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang, 050024, People's Republic of China.
Yanli
Y
Zeng
Institute of Computational Quantum Chemistry, College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang, 050024, People's Republic of China.
Xiaoyan
X
Li
Institute of Computational Quantum Chemistry, College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang, 050024, People's Republic of China.
Zheng
Z
Sun
Institute of Computational Quantum Chemistry, College of Chemistry and Material Science, Hebei Normal University, Shijiazhuang, 050024, People's Republic of China.
Lingpeng
L
Meng
D002244:Carbon / Q000737:chemistry*; D006219:Halogens / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry*; D011789:Quantum Theory; D055672:Static Electricity
D006219:Halogens; D010720:Phosphines; D002244:Carbon; D009584:Nitrogen; D010100:Oxygen
density difference; halogen bond; molecular electrostatic potentials; polarizable interaction; σ-hole interaction