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Cooperative effect of hetero-nuclear MnNi+ cation enhancing C–H bond activation of cyclohexane: a theoretical study

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Abstract

Hetero-nuclear MnNi+ cation exhibits high catalytic activity in the C–H bond activation of cyclohexane in comparison with mono-nuclear Mn+ cation. The dehydrogenation reaction mechanistic investigations of cyclohexane catalyzed by MnNi+ and Mn+ have been carried out with density functional theory calculations. The activations of the first, third and fifth C–H bond of cyclohexane occur mainly because of the orbital interaction between the C–H σ bond of cyclic hydrocarbon and the empty d orbital of Mn. The smaller energy gaps of interacting orbitals result in stronger electron transfer between the related orbitals, which can elucidate MnNi+ cation is more reactive than Mn+. The coordination bonds between MnNi+ and cycloolefin in the second and third dehydrogenation processes of cyclohexane are another important factor for accelerating the dehydrogenation, which can stabilize the transition states for the activation of C–H bonds. The lower the transition state energy, the easier the C–H bond activation.

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Authors and Affiliations

  1. Gansu Key Laboratory of Polymer Materials, College of Chemistry and Chemical Engineering, Key Laboratory of Eco-functional Polymer Materials of the Ministry of Education, Northwest Normal University, Lanzhou, 730070, Gansu, People’s Republic of China

    Feng Lu, Li Li, Xiaoxia Zhang, Yuxiu Nie & Zhiyuan Geng

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  1. Feng Lu
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  2. Li Li
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  3. Xiaoxia Zhang
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Lu, F., Li, L., Zhang, X. et al. Cooperative effect of hetero-nuclear MnNi+ cation enhancing C–H bond activation of cyclohexane: a theoretical study. Theor Chem Acc 139, 48 (2020). https://doi.org/10.1007/s00214-020-2562-7

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