Effect of the Ligand Backbone on the Reactivity and Mechanistic Paradigm of Non-Heme Iron(IV)-Oxo during Olefin Epoxidation

The oxygen atom transfer (OAT) reactivity of the non-heme [Fe-IV(2PyN2Q)(O)](2+) (2) containing the sterically bulky quinoline-pyridine pentadentate ligand (2PyN2Q) has been thoroughly studied with different olefins. The ferryl-oxo complex 2 shows excellent OAT reactivity during epoxidations. The steric encumbrance and electronic effect of the ligand influence the mechanistic shuttle between OAT pathway I and isomerization pathway II (during the reaction stereo pure olefins), resulting in a mixture of cis-trans epoxide products. In contrast, the sterically less hindered and electronically different [Fe-IV(N4Py)(O)](2+) (1) provides only cis-stilbene epoxide. A Hammett study suggests the role of dominant inductive electronic along with minor resonance effect during electron transfer from olefin to 2 in the rate-limiting step. Additionally, a computational study supports the involvement of stepwise pathways during olefin epoxidation. The ferryl bend due to the bulkier ligand incorporation leads to destabilization of both dz2 and dx2-y2 orbitals, leading to a very small quintet-triplet gap and enhanced reactivity for 2 compared to 1. Thus, the present study unveils the role of steric and electronic effects of the ligand towards mechanistic modification during olefin epoxidation

Automated summary

The study reveals that the steric and electronic effects of the non-heme ligand play a crucial role in influencing the mechanism of oxygen atom transfer reactions in olefin epoxidation, leading to the formation of different epoxide products with distinct stereochemistry. Additionally, the dominant inductive electronic effect and minor resonance effect are observed in the rate-limiting step, highlighting their contributions to electron transfer from olefin to the ferryl oxo complex.