Structural diversity of metallacycle intermediates for ethylene dimerization on heterogeneous NiMCM-41 catalyst: a quantum chemical perspective


Nanocluster models were investigated to explore the diversity of metallacycle intermediates for ethylene dimerization over NiMCM-41 at B3LYP/6-311+G* and M06/Def2-TZVP. The thermodynamic favorability of the formation of matallacycle with respect to the ring size of silica varied in the sequence of 6T < 3T < 2T < 5T < 4T in terms of Gibbs free energy (ranging from − 10.01 to 16.66 kcal/mol at B3LYP/6-311+G*). The reaction cycle faced lower barriers on 3T and 2T clusters, however. The formation of the intermediate and π complexation of 1-butene led to positive total charges on the hydrocarbon segment of the complex, being maximized on four-membered sites and minimized on two-membered ones. Further insights are also provided with QTAIM, frontier orbital, and FTIR analyses.

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Correspondence to Mohammad Ghashghaee or Zahra Azizi.

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Ghambarian, M., Ghashghaee, M., Azizi, Z. et al. Structural diversity of metallacycle intermediates for ethylene dimerization on heterogeneous NiMCM-41 catalyst: a quantum chemical perspective. Struct Chem 30, 137–150 (2019).

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  • Metallacycle
  • Dimerization
  • Nickel
  • DFT
  • Nanocluster
  • Thermochemistry
  • Ethylene
  • Structure
  • Thermodynamics
  • Energetics
  • Catalyst
  • Butene
  • Kinetics
  • Energy barrier
  • Free energy span
  • MCM-41
  • Silica
  • Oligomerization
  • Petrochemistry
  • NBO
  • AIM
  • Molecular orbital
  • Olefin