A theoretical thermodynamic investigation of cascade reactions in dinuclear octa-azacryptates involving carbon dioxide

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Title: A theoretical thermodynamic investigation of cascade reactions in dinuclear octa-azacryptates involving carbon dioxide
Authors: English, Niall J.Mooney, Damian A.
Permanent link: http://hdl.handle.net/10197/2877
Date: 2011
Online since: 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.
Funding Details: Science Foundation Ireland
Other funder
metadata.dc.description.othersponsorship: 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
Keywords: Density functional theoryThermodynamic parametersCO2 fixationDinuclear cryptatesNBO analysis
Subject LCSH: Density functionals
Carbon cycle (Biogeochemistry)
DOI: 10.1007/s00894-011-0965-z
Other versions: http://dx.doi.org/10.1007/s00894-011-0965-z
Language: en
Status of Item: Peer reviewed
Appears in Collections:Solar Energy Conversion (SEC) Cluster Research Collection
Chemical and Bioprocess Engineering Research Collection

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