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Investigation of agostic interaction through NBO analysis and its impact on β-hydride elimination and dehydrogenation: a DFT approach

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Abstract

Agostic interactions have been investigated through NBO analysis tuning each part of H2LMMZCHR2 by varying metal centre and intramolecular groups in different positions of the molecule. We have calculated the energy transfer phenomena between donor and acceptor orbitals associated with the agostic bond by second-order perturbation analysis and characterized the acceptor orbitals for whether it is a vacant metal lone pair or molecular orbital associated with both metal and ligand. The investigation of agostic phenomenon by altering the orientation of the metal-associated ligand is another aspect of this work to reveal the orientation effect as one of the controlling factors of the agostic interaction. We have further studied the impact of agostic interaction on the two well-recognized reaction processes, namely β-hydride elimination and dehydrogenation for all the d0 systems under investigation. Both the reactions are found to be facilitated by agostic interaction, where the nature of agostic hydrogen varies from reaction to reaction. The complete work furnishes both characterization and reaction pathways to portray agostic phenomena by interconnecting the molecular geometry with the reaction processes.

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Acknowledgments

TD, TA and TB are grateful to the Council of Scientific and Industrial Research (CSIR), Government of India, for providing them research fellowships. AKD gratefully acknowledges a research grant under scheme number: SB/S1/PC-79/2012 from the Department of Science and Technology (DST), Govt. of India.

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Authors and Affiliations

  1. Indian Association for the Cultivation of Science, Jadavpur, Kolkata, 700032, India

    Tanay Debnath, Tamalika Ash, Tahamida Banu & Abhijit K. Das

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  1. Tanay Debnath
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  2. Tamalika Ash
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  3. Tahamida Banu
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  4. Abhijit K. Das
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Correspondence to Abhijit K. Das.

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214_2016_1939_MOESM1_ESM.docx

Figures of the products obtained from β-hydride elimination and dehydrogenation and Table of NPA charges of all the reactants, TSs and products of both reaction processes. (DOCX 919 kb)

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Debnath, T., Ash, T., Banu, T. et al. Investigation of agostic interaction through NBO analysis and its impact on β-hydride elimination and dehydrogenation: a DFT approach. Theor Chem Acc 135, 175 (2016). https://doi.org/10.1007/s00214-016-1939-0

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