Physical nature of substituent effects in XH/π interactions

Jacob W G Bloom, Rajesh K. Raju, Steven E. Wheeler

Research output: Contribution to journalArticle

65 Citations (Scopus)

Abstract

XH/Π interactions (e.g.: CH/Π, OH/Π, etc.) are ubiquitous in chemical and biochemical contexts. Although there have been many studies of substituent effects in XH/Π interactions, there have been only limited systematic studies covering a broad range of substituents. We provide a comprehensive and systematic study aimed at unraveling the nature of aryl substituent effects on model BH/Π, CH/Π, NH/Π, OH/Π, and F/Π interactions (e.g.: BH 3⋯C 6H 5Y, CH 4⋯C 6H 5Y, etc.) based on estimated CCSD(T)/aug-cc-pVTZ interaction energies as well as symmetry-adapted perturbation theory (SAPT) results. We show that the impact of substituents on XH/Π interactions depends strongly on the identity of the XH group, and the strength of these effects increases with increasing polarization of the XH bond. Overall, the results are in accord with previous work and follow expected trends from basic physical principles. That is, electrostatic effects dominate the substituent effects for the polar XH/Π interactions (NH/Π, OH/Π, and FH/Π), while dispersion effects are more important for the nonpolar BH/Π and CH/Π interactions. The electrostatic component of these interactions is shown to correlate well with Hammett constants (σ m), while accounting for the dispersion component requires consideration of molar refractivities (MR) and interaction distances concurrently. The correlation of the dispersion component of these interactions with MR values alone is rather weak.

Original languageEnglish
Pages (from-to)3167-3174
Number of pages8
JournalJournal of Chemical Theory and Computation
Volume8
Issue number9
DOIs
Publication statusPublished - 11 Sep 2012
Externally publishedYes

Fingerprint

Electrostatics
Refractive index
interactions
methylidyne
Polarization
refractivity
electrostatics
coverings
perturbation theory
trends
symmetry
polarization
energy

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

Cite this

Physical nature of substituent effects in XH/π interactions. / Bloom, Jacob W G; Raju, Rajesh K.; Wheeler, Steven E.

In: Journal of Chemical Theory and Computation, Vol. 8, No. 9, 11.09.2012, p. 3167-3174.

Research output: Contribution to journalArticle

Bloom, Jacob W G ; Raju, Rajesh K. ; Wheeler, Steven E. / Physical nature of substituent effects in XH/π interactions. In: Journal of Chemical Theory and Computation. 2012 ; Vol. 8, No. 9. pp. 3167-3174.
@article{e02b38f385d44412916f0182f8d616a7,
title = "Physical nature of substituent effects in XH/π interactions",
abstract = "XH/Π interactions (e.g.: CH/Π, OH/Π, etc.) are ubiquitous in chemical and biochemical contexts. Although there have been many studies of substituent effects in XH/Π interactions, there have been only limited systematic studies covering a broad range of substituents. We provide a comprehensive and systematic study aimed at unraveling the nature of aryl substituent effects on model BH/Π, CH/Π, NH/Π, OH/Π, and F/Π interactions (e.g.: BH 3⋯C 6H 5Y, CH 4⋯C 6H 5Y, etc.) based on estimated CCSD(T)/aug-cc-pVTZ interaction energies as well as symmetry-adapted perturbation theory (SAPT) results. We show that the impact of substituents on XH/Π interactions depends strongly on the identity of the XH group, and the strength of these effects increases with increasing polarization of the XH bond. Overall, the results are in accord with previous work and follow expected trends from basic physical principles. That is, electrostatic effects dominate the substituent effects for the polar XH/Π interactions (NH/Π, OH/Π, and FH/Π), while dispersion effects are more important for the nonpolar BH/Π and CH/Π interactions. The electrostatic component of these interactions is shown to correlate well with Hammett constants (σ m), while accounting for the dispersion component requires consideration of molar refractivities (MR) and interaction distances concurrently. The correlation of the dispersion component of these interactions with MR values alone is rather weak.",
author = "Bloom, {Jacob W G} and Raju, {Rajesh K.} and Wheeler, {Steven E.}",
year = "2012",
month = "9",
day = "11",
doi = "10.1021/ct300520n",
language = "English",
volume = "8",
pages = "3167--3174",
journal = "Journal of Chemical Theory and Computation",
issn = "1549-9618",
publisher = "American Chemical Society",
number = "9",

}

TY - JOUR

T1 - Physical nature of substituent effects in XH/π interactions

AU - Bloom, Jacob W G

AU - Raju, Rajesh K.

AU - Wheeler, Steven E.

PY - 2012/9/11

Y1 - 2012/9/11

N2 - XH/Π interactions (e.g.: CH/Π, OH/Π, etc.) are ubiquitous in chemical and biochemical contexts. Although there have been many studies of substituent effects in XH/Π interactions, there have been only limited systematic studies covering a broad range of substituents. We provide a comprehensive and systematic study aimed at unraveling the nature of aryl substituent effects on model BH/Π, CH/Π, NH/Π, OH/Π, and F/Π interactions (e.g.: BH 3⋯C 6H 5Y, CH 4⋯C 6H 5Y, etc.) based on estimated CCSD(T)/aug-cc-pVTZ interaction energies as well as symmetry-adapted perturbation theory (SAPT) results. We show that the impact of substituents on XH/Π interactions depends strongly on the identity of the XH group, and the strength of these effects increases with increasing polarization of the XH bond. Overall, the results are in accord with previous work and follow expected trends from basic physical principles. That is, electrostatic effects dominate the substituent effects for the polar XH/Π interactions (NH/Π, OH/Π, and FH/Π), while dispersion effects are more important for the nonpolar BH/Π and CH/Π interactions. The electrostatic component of these interactions is shown to correlate well with Hammett constants (σ m), while accounting for the dispersion component requires consideration of molar refractivities (MR) and interaction distances concurrently. The correlation of the dispersion component of these interactions with MR values alone is rather weak.

AB - XH/Π interactions (e.g.: CH/Π, OH/Π, etc.) are ubiquitous in chemical and biochemical contexts. Although there have been many studies of substituent effects in XH/Π interactions, there have been only limited systematic studies covering a broad range of substituents. We provide a comprehensive and systematic study aimed at unraveling the nature of aryl substituent effects on model BH/Π, CH/Π, NH/Π, OH/Π, and F/Π interactions (e.g.: BH 3⋯C 6H 5Y, CH 4⋯C 6H 5Y, etc.) based on estimated CCSD(T)/aug-cc-pVTZ interaction energies as well as symmetry-adapted perturbation theory (SAPT) results. We show that the impact of substituents on XH/Π interactions depends strongly on the identity of the XH group, and the strength of these effects increases with increasing polarization of the XH bond. Overall, the results are in accord with previous work and follow expected trends from basic physical principles. That is, electrostatic effects dominate the substituent effects for the polar XH/Π interactions (NH/Π, OH/Π, and FH/Π), while dispersion effects are more important for the nonpolar BH/Π and CH/Π interactions. The electrostatic component of these interactions is shown to correlate well with Hammett constants (σ m), while accounting for the dispersion component requires consideration of molar refractivities (MR) and interaction distances concurrently. The correlation of the dispersion component of these interactions with MR values alone is rather weak.

UR - http://www.scopus.com/inward/record.url?scp=84866157914&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84866157914&partnerID=8YFLogxK

U2 - 10.1021/ct300520n

DO - 10.1021/ct300520n

M3 - Article

AN - SCOPUS:84866157914

VL - 8

SP - 3167

EP - 3174

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

SN - 1549-9618

IS - 9

ER -