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The addition reactions between N-heterocyclic carbenes and fullerenes (C60 and C70): a density functional study

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Abstract

The potential energy surfaces for the addition reactions of N-heterocyclic carbene with C60 and C70 are characterized in detail, using density functional theory (M06-2X). These theoretical investigations strongly suggest that the one-point attack in formation of the single-bonded adduct is the most favorable reaction pathway at room temperature, rather than the production of the cycloadduct with a three-membered ring, from both kinetic and thermodynamic viewpoints. Also, this theoretical work indicates that the dispersion interactions cannot make the contributions to determine the regioselective formations for these NHC–fullerene Lewis acid–base adducts. These theoretical conclusions are consistent with the available experimental observations.

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Notes

  1. The LANL2DZdp basis sets for C, N, and H were obtained from the Extensible Computational Chemistry Environment Basis Set Database (http://www.emsl.pnl.gov/forms/basisform.html), as and distributed by the Molecular Science Computing Facility, Environmental and Molecular Sciences Laboratory.

  2. Vibrational frequency calculations at the RHF/LANL2DZ level were used to characterize all the stationary points as either minima (no imaginary frequencies) or transition states (one imaginary frequency). Then these stationary points were further calculated at the M06-2X/LANL2DZdp level using the opt=readfc keyword. Due to the limitation of both available CPU time and memory size, the M06-2X zero-point energy could not be applied for all of the IDipp–C60 and IDipp–C70 systems in the present work. That is, because frequencies were not calculated for all species at the M06-2X/LANL2DZdp level of theory, zero-point energy corrections were not performed. Nevertheless, the addition of these corrections would not change our conclusions.

  3. The four types of geometrical results are found as follows: (i) the 6–6-bridged mono-adduct of C60 with a closed trans-annular bond, (ii) the 5–6-bridged molecule with an open trans-annular structure, (iii) the 6–6-bridged compound with an open trans-annular structure and (iv) the 5–6-bridged compound with a closed trans-annular bond. See reference [3].

  4. The pyramidalization angles are measured to be 11.9°, 11.9°, 11.4°, 10.2° and 8.7° for C(a), C(b), C(c), C(d), and C(e), respectively [7].

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Acknowledgments

The authors are grateful to the National Center for High-Performance Computing of Taiwan for generous amounts of computing time. They also thank the Ministry of Science and Technology of Taiwan for the financial support. Special thanks are also due to Reviewers 1 and 2 for very helpful suggestions and comments.

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Authors and Affiliations

  1. Department of Applied Chemistry, National Chiayi University, Chiayi, 60004, Taiwan

    Ming-Chung Li & Ming-Der Su

  2. Department of Medicinal and Applied Chemistry, Kaohsiung Medical University, Kaohsiung, 80708, Taiwan

    Ming-Der Su

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  1. Ming-Chung Li
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  2. Ming-Der Su
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Correspondence to Ming-Der Su.

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Li, MC., Su, MD. The addition reactions between N-heterocyclic carbenes and fullerenes (C60 and C70): a density functional study. Theor Chem Acc 134, 38 (2015). https://doi.org/10.1007/s00214-015-1629-3

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