Theoretical analysis of cooperative effects of small molecule activation by frustrated Lewis pairs

The energy profiles of the activation reaction of small molecules (H 2 , Br 2 and CO 2 ) with boron/phosphorus frustrated Lewis pairs (FLPs) have been calculated with dispersion corrected DFT (TPSS-D3). We have investigated the cooperative nature of the reactions by analyzing interaction energies in...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2012-08, Vol.41 (3), p.9111-9118
Main Authors: Mück-Lichtenfeld, Christian, Grimme, Stefan
Format: Article
Language:English
Subjects:
Activation analysis
Activation energy
Carbon dioxide
Density
Dispersions
Mathematical analysis
Representations
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Summary:The energy profiles of the activation reaction of small molecules (H 2 , Br 2 and CO 2 ) with boron/phosphorus frustrated Lewis pairs (FLPs) have been calculated with dispersion corrected DFT (TPSS-D3). We have investigated the cooperative nature of the reactions by analyzing interaction energies in the ternary system and for reactant pairs. The non-additive contributions to the total interaction energy add to the driving force of the activation reaction, even at early stages of the process. We propose the isosurface representation of the many-body deformation density Δ ρ mb as a qualitative tool to visualize cooperative, non-additive effects in complex chemical systems. The cooperative nature of small molecule activation with FLPs is analysed in terms of many-body contributions to energy and deformation density.
ISSN:1477-9226
1477-9234
DOI:10.1039/c2dt30562c