We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
Cooperative effect of hetero-nuclear MnNi+ cation enhancing C–H bond activation of cyclohexane: a theoretical study.
- Authors
Lu, Feng; Li, Li; Zhang, Xiaoxia; Nie, Yuxiu; Geng, Zhiyuan
- 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.
- Subjects
CARBON-hydrogen bonds; ORBITAL interaction; DEHYDROGENATION; DENSITY functional theory; CHARGE exchange; CATIONS; CYCLOHEXANE
- Publication
Theoretical Chemistry Accounts: Theory, Computation, & Modeling, 2020, Vol 139, Issue 3, p1
- ISSN
1432-881X
- Publication type
Article
- DOI
10.1007/s00214-020-2562-7