Journal of Molecular Modeling

, Volume 17, Issue 12, pp 3151–3162 | Cite as

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

  • Morad M. El-Hendawy
  • Niall J. English
  • Damian A. Mooney
Original Paper

Abstract

This paper investigates the thermodynamics of gas-phase CO2 cascade uptake-reactions in the form of carbonate or monomethylcarbonate anions in the host cavity of various dinuclear octa-azacryptates of m-CH2C6H4CH2 and 2,5-furano-spaced hosts, L 1 and L 2 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 were also investigated to determine the parameters that affect the stability of the complexes. Natural bond orbital (NBO) analysis was used to investigate the interactions between the trapped anion and its host. Ion selectivity was studied in terms of the formation of dinuclear cryptate complexes, while the basicity and nucleophilicity of cryptands towards Lewis acids was also studied, and good agreement was found vis-à-vis available experimental data.

Figure

Syn-anti μ-η1, η2 arrangement of monomethylcarbonate arrangement within the host cavity of [Cu2L1MeCO3]3+

Keywords

DFT CO2 fixation Dinuclear cryptates Thermodynamic parameters NBO analysis 

Notes

Acknowledgments

The authors acknowledge useful conversations with Dr. Grace Morgan. This material is based upon works supported by Science Foundation Ireland (SFI) under Grant No. [07/SRC/B1160]. We also thank SFI and the Irish Center for High-End Computing for the provision of high-performance computing facilities.

Supplementary material

894_2011_965_MOESM1_ESM.doc (246 kb)
ESM 1 (DOC 245 kb)

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Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Morad M. El-Hendawy
    • 1
  • Niall J. English
    • 1
  • Damian A. Mooney
    • 1
  1. 1.The SFI Strategic Research Cluster in Solar Energy Conversion and the Center for Synthesis and Chemical Biology, School of Chemical and Bioprocess EngineeringUniversity College DublinDublin 4Ireland

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