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

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.