Understanding the Reactivity of Planar Polycyclic Aromatic Hydrocarbons: Towards the Graphene Limit
Open Access
- 15 June 2016
- journal article
- research article
- Published by Wiley in Chemistry – A European Journal
- Vol. 22 (30), 10572-10580
- https://doi.org/10.1002/chem.201600900
Abstract
The Diels–Alder reactivity of maleic anhydride towards the bay regions of planar polycyclic aromatic hydrocarbons was explored computationally in the DFT framework. The process becomes more and more exothermic and the associated activation barriers become lower and lower when the size of the system increases. This enhanced reactivity follows an exponential behavior that reaches its maximum for systems having 18–20 benzenoid rings in their structures. This peculiar behavior was analyzed in detail by using the activation strain model of reactivity in combination with energy decomposition analysis. The influence of the change in the aromaticity of the polycyclic compound during the process on the respective activation barriers was also studied.Keywords
Funding Information
- Spanish MINECO
- FEDER (CTQ2013-44303-P, CTQ2014-51912-REDC, CTQ2014-54306-P, UNGI10-4E-801)
- Fundación BBVA
- Catalan DIUE (2014SGR931, XRQTC)
- icrea
- MINECO
This publication has 61 references indexed in Scilit:
- Reactivity and Selectivity of Bowl‐Shaped Polycyclic Aromatic Hydrocarbons: Relationship to C60Chemistry – A European Journal, 2015
- The activation strain model and molecular orbital theoryWIREs Computational Molecular Science, 2015
- Chemistry at the interior atoms of polycyclic aromatic hydrocarbonsChemical Society Reviews, 2015
- Understanding Trends in Reaction BarriersPublished by Wiley ,2014
- The activation strain model and molecular orbital theory: understanding and designing chemical reactionsChemical Society Reviews, 2014
- A review of airborne polycyclic aromatic hydrocarbons (PAHs) and their human health effectsEnvironment International, 2013
- Chemical reactivity and long-range transport potential of polycyclic aromatic hydrocarbons – a reviewChemical Society Reviews, 2013
- Energy decomposition analysisWIREs Computational Molecular Science, 2011
- The activation strain model of chemical reactivityOrganic & Biomolecular Chemistry, 2010
- Understanding reactivity with Kohn-Sham molecular orbital theory: E2-SN2 mechanistic spectrum and other conceptsJournal of Computational Chemistry, 1999