English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  Balancing Donor‐Acceptor and Dispersion Effects in Heavy Main Group Element π Interactions: Effect of Substituents on the Pnictogen···π Arene Interaction

Krasowska, M., Fritzsche, A.-M., Mehring, M., & Auer, A. A. (2019). Balancing Donor‐Acceptor and Dispersion Effects in Heavy Main Group Element π Interactions: Effect of Substituents on the Pnictogen···π Arene Interaction. ChemPhysChem, 20(19), 2539-2552. doi:10.1002/cphc.201900747.

Item is

Basic

show hide
Genre: Journal Article

Files

show Files

Locators

show

Creators

show
hide
 Creators:
Krasowska, Małgorzata1, Author           
Fritzsche, Ana-Maria2, Author
Mehring, Michael2, Author
Auer, Alexander A.1, Author           
Affiliations:
1Research Group Auer, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541705              
2Technische Universität Chemnitz, Straße der Nationen 62, 09107 Chemnitz, GERMANY, ou_persistent22              

Content

show
hide
Free keywords: ab-initio calculations; computational chemistry; intermolecular interactions; organometallic chemistry; pnictogen compounds
 Abstract: High‐level ab initio calculations using the DLPNO‐CCSD(T) method in conjunction with the local energy decomposition (LED) were performed to investigate the nature of the intermolecular interaction in the bismuth trichloride adducts with π arene systems. Special emphasis was put on the effect of the substituent in the aromatic ring. For this purpose, benzene derivatives with one or three substituents (R = NO2, CF3, OCHO, OH and NH2) were chosen and their influence on donor‐acceptor interaction was examined. Local energy decomposition was performed in order to gain deeper insight into the composition of the interaction. Additionally, the study was extended to the intermolecular adducts of arsenic and antimony trichloride with benzene derivatives having one substituent (R = NO2 and NH2) in order to rationalize trends in the periodic table. The analysis of natural charges and frontier molecular orbitals shows that donor‐acceptor interactions are of π→σ* type and that their strength correlates with charge transfer and orbital energy differences. An analysis of different bonding motifs (Bi···π arene, Bi···R and Cl···π arene) shows that if dispersion and donor‐acceptor interaction coincide as the donor highest occupied molecular orbital (HOMO) of the arene is delocalized over the π system, the M···π arene motif is preferred. If the donor HOMO is localized on the substituent, R···π arene bonding motifs are preferred. The Cl···π arene bonding motif is the least favorable with the lowest overall interaction energy.

Details

show
hide
Language(s): eng - English
 Dates: 2019-07-292019-08-012019-10-02
 Publication Status: Published online
 Pages: 14
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1002/cphc.201900747
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: ChemPhysChem
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: Weinheim, Germany : Wiley-VCH
Pages: - Volume / Issue: 20 (19) Sequence Number: - Start / End Page: 2539 - 2552 Identifier: ISSN: 1439-4235
CoNE: https://pure.mpg.de/cone/journals/resource/954925409790