P. V. Ivchenko, D. A. Pyatakov, A. N. Tavtorkin, I. E. Nifant'ev, “DFT probe and visualization of the mechanisms of BF<sub>3</sub>-catalyzed cationic oligomerization of olefins”, Mendeleev Commun., 2025, Volume 35, Issue 4,Pages <nobr>404

Communications

DFT probe and visualization of the mechanisms of BF₃-catalyzed cationic oligomerization of olefins

P. V. Ivchenko^ab, D. A. Pyatakov^a, A. N. Tavtorkin^a, I. E. Nifant'ev^ab

^a A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 119991 Moscow, Russian Federation
^b Department of Chemistry, M. V. Lomonosov Moscow State University, 119991 Moscow, Russian Federation

Abstract: The mechanisms of BF₃/PrⁱOH catalyzed oligomerization of isobutylene, dec-1-ene and methyl undec-10-enoate were analyzed using DFT modeling. The newly developed concept implies the participation of two olefin molecules and complex (BF₃ · ROH)₂ as an initiator, the role of the ether additives is to provide high exo-selectivity of isobutylene oligomerization. This concept argues the chain-growth oligomerization with intermediate retention of the cationic center (isobutylene), or H⁺ elimination (linear α-olefins) explaining the preferable formation of trimers.

Keywords: BF₃, carbenium ions, cationic oligomerization, dec-1-ene, DFT, isobutylene, polar vinyl monomers.

Received: 21.11.2024
Accepted: 28.01.2025

Language: English

DOI: 10.71267/mencom.7687

	*Supplementary materials:*
		Supplementary_data_1.pdf	2.3 Mb