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A theoretical thermodynamic investigation of cascade reactions in dinuclear octa-azacryptates involving carbon dioxide
Author(s)
Date Issued
2011
Date Available
2011-03-24T17:06:29Z
Abstract
This paper investigates the thermodynamics of gas-phase CO2 cascade uptake-reactions in the form of carbonate or methoxycarbonate anions in the host cavity of various dinuclear octa-azacryptates of m-CH2C6H4CH2 and 2,5-furano-spaced hosts, L1 and L2 cryptands, using density functional theory (DFT). The cascade process involves two stages, namely the formation of dinuclear cryptate complexes and the subsequent formation of either μ-carbonato cryptate complexes or μ-monomethylcarbonato cryptates. The geometric and electronic structures are also investigated to determine the parameters which affect the stability of the complexes. Natural bond orbital (NBO) analysis has been used to investigate the interactions between the trapped anion and its host. The ion selectivity has been studied in terms of the formation of dinuclear crypate complexes, while the basicity and nucleophilicity of cryptands towards Lewis acids have also been studied, and good agreement was found vis-à -vis available experimental data.
Sponsorship
Science Foundation Ireland
Other funder
Other Sponsorship
Irish Centre for High End Computing
Type of Material
Journal Article
Publisher
Springer
Journal
Journal of Molecular Modelling
Volume
17
Issue
12
Start Page
3151
End Page
3162
Copyright (Published Version)
2011 Springer-Verlag
Subject – LCSH
Density functionals
Carbon cycle (Biogeochemistry)
Thermodynamics
Web versions
Language
English
Status of Item
Peer reviewed
ISSN
1610-2940 (Print)
0948-5023 (Online)
This item is made available under a Creative Commons License
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