Journal of Molecular Graphics and Modelling
Journal of Molecular Graphics and Modelling
3 years ago

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

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.

Publisher URL: www.sciencedirect.com/science

DOI: S1093326317303637

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.