A theoretical survey of substituent effects on the properties of pnicogen and hydrogen bonds in cationic complexes of PH4+ with substituted benzonitrile.

In this paper, we analyze the substituent effects on the nature and characteristics of P⋯N and H⋯N interactions in X-PhCN:PH4+ complexes (X=H, F, Cl, Br, CN, NH2, NO2, CH3 and N(CH3)2) as a working model at MP2(FC)/6-311++G(d,p) level of theory. The natural bond orbital (NBO) method as well as the quantum theory of atoms in molecules (AIM) is applied to characterize interactions in the studied complexes. In general, the pnicogen bonded systems are more stable than the corresponding hydrogen bonded cases. The strength of the interactions generally correlates well with the magnitudes of the negative electrostatic potentials of the nitrogen atom of isolated substituted benzonitrile (Vs,min(N)). The results indicate that increase in the electron withdrawing power of substituents is accompanied by decrease in the absolute value of Vs,min(N). Also, there are meaningful relationships between Vs,min(N) values and the results of AIM and NBO analyses in studied systems. Moreover, it is found that substituent effects on characteristics of P⋯N pnicogen and H⋯N hydrogen bonds can be expressed by Hammett constants. Copyright © 2017 Elsevier Inc. All rights reserved.

Citation

Sotoodeh Bagheri, Hamid Reza Masoodi, Ali Reza Akrami-Mohajeri. A theoretical survey of substituent effects on the properties of pnicogen and hydrogen bonds in cationic complexes of PH4+ with substituted benzonitrile. Journal of molecular graphics & modelling. 2017 Oct;77:64-71

PMID: 28841462

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