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Can a decrease in anti-aromaticity increase the dihydrogen activation ability of a frustrated phosphorous/borane Lewis pair?: a DFT study

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Abstract

The mechanism of dihydrogen activation has been theoretically investigated by means of DFT calculation. An experimentally synthesized bridged P/B frustrated Lewis pair (FLP) and two designed FLPs are used for this purpose. The model FLPs 2 and 3 are more efficient than FLP 1 for H2 activation as revealed by the thermochemical and kinetic data. A significant amount of electron density is transferred from H2 molecule to the FLPs at the transition states (TSs) during the process of H2 activation, and this is greater at the corresponding TSs of FLPs 2 and 3 than that of FLP 1. The NICS(0) and NICS(1zz) of the boron heterocycle at the FLPs 2 and 3, and at the corresponding TSs and the product geometries of H2 activation demonstrate that the anti-aromatic character of the rings in the FLPs is remarkably reduced at the TSs and finally at the products and that is most likely responsible for enhanced activity of FLPs 2 and 3 by decreasing the activation barrier.

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Acknowledgements

We are delighted to dedicate this article to Professor Ramon Carbó-Dorca on his 80th birth anniversary. We would like to thank Professors Gernot Frenking, Miquel Solà and Tanmoy Chakraborty for kindly inviting us to contribute this article to the Special Issue of the Theoretical Chemistry Accounts. PKC thanks the DST, New Delhi, for his J. C. Bose National Fellowship.

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  1. Department of Chemistry and Center for Theoretical Studies, Indian Institute of Technology Kharagpur, Kharagpur, 721302, India

    Manas Ghara & Pratim Kumar Chattaraj

  2. Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, 400076, India

    Pratim Kumar Chattaraj

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Ghara, M., Chattaraj, P.K. Can a decrease in anti-aromaticity increase the dihydrogen activation ability of a frustrated phosphorous/borane Lewis pair?: a DFT study. Theor Chem Acc 139, 183 (2020). https://doi.org/10.1007/s00214-020-02698-6

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