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A multiscale ONIOM study of the buckminsterfullerene (C60) Diels–Alder reaction: from model design to reaction path analysis

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Abstract

The hybrid ONIOM (Our own N-layered Integrated molecular Orbital and molecular Mechanics) formalism is employed to investigate the Diels–Alder reaction of the buckminsterfullerene C60. Our computations suggest that the ONIOM2(M06-2X/6-31G(d): SVWN/STO-3G) model, enclosing both the diene and the pyracyclene fragment of C60 in the higher-layer, provides a reasonable trade-off between accuracy and computational cost as it comes to predicting reaction energetics. Moreover, the frontier molecular orbital (FMO) theory and activation strain model (ASM) are jointly relied on to rationalize the effect of –OH and –CN substituents on the activation barrier of this reaction. Finally, reaction paths are scrutinized to get insight into the various forces underpinning the process of cycloadduct formation.

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Acknowledgements

This work was supported by the BEBUC Scholarship system through the funding granted by Else-Kroener-Fresenius Stiftung. Bienfait K. Isamura is grateful to the Center for High Performance Computing (CHPC) for having provided the resources used to carry out this study (project CHEM0802) and the faculty of science (Rhodes University) for the science discretionary grant (SD06/2022). He also thanks Dr. Zainab Sanusi and Dr. Tshiwawa Tendamudzimu for having read the manuscript.

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  1. Department of Chemistry, Rhodes University, Eastern Cape, Makhanda, 6140, South Africa

    Bienfait Kabuyaya Isamura & Kevin Alan Lobb

  2. Research Unit in Bioinformatics (RUBi), Rhodes University, Eastern Cape, Makhanda, 6140, South Africa

    Kevin Alan Lobb

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  1. Bienfait Kabuyaya Isamura
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B.K. Isamura: methodology, investigation, formal analysis, writing—original draft. K.A. Lobb: conceptualization, supervision, funding acquisition, writing—review and editing. All the authors approved the current version of this manuscript.

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Correspondence to Bienfait Kabuyaya Isamura.

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Isamura, B.K., Lobb, K.A. A multiscale ONIOM study of the buckminsterfullerene (C60) Diels–Alder reaction: from model design to reaction path analysis. J Mol Model 28, 327 (2022). https://doi.org/10.1007/s00894-022-05319-0

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