The Journal of Physical Chemistry A, Journal Year: 2025, Volume and Issue: unknown

Published: March 2, 2025

The mechanisms of iron-catalyzed [4 + 2] cycloadditions unactivated dienes were investigated using density functional theory calculations. calculation results show that the reaction involves sequential key steps an initial ligand exchange followed by oxidative coupling, isomerization to form a seven-membered ferracycle intermediate, and C-C reductive elimination cyclohexene product. step is shown be rate-determining catalytic cycle. Moreover, energy profiles with three possible spin states (SFe = 0, 1, 2) have been considered. crossing occurs mainly through quintet intermediates triplet transition states, which indicates has two-state reactivity. In addition, origins chemical selectivities enantioselectivities are analyzed in detail. It was found spatial effect between catalyst substrate leads high chemoselectivity, while stabilizing attractive interaction enantioselectivity.

Language: Английский