Structural Chemistry

, Volume 30, Issue 1, pp 137–150 | Cite as

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

  • Mehdi Ghambarian
  • Mohammad GhashghaeeEmail author
  • Zahra AziziEmail author
  • Mahboobeh Balar
Original Research


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.


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 



This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

11224_2018_1184_MOESM1_ESM.pdf (109 kb)
ESM 1 (PDF 109 kb)


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Authors and Affiliations

  1. 1.Gas Conversion Department, Faculty of PetrochemicalsIran Polymer and Petrochemical InstituteTehranIran
  2. 2.Faculty of PetrochemicalsIran Polymer and Petrochemical InstituteTehranIran
  3. 3.Department of Chemistry, Karaj BranchIslamic Azad UniversityKarajIran

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