# Effect of the [Fe(salen)]2‑μ-oxo Catalyst Electronic Structure on Reductive Hydroamination

## TL;DR

This paper studies how the electronic structure of a specific iron catalyst affects its performance in a chemical reaction called reductive hydroamination.

## Contribution

The study introduces three electronically distinct [Fe(salen)]2-μ-oxo complexes and shows how ligand electronics influence catalytic efficiency.

## Key findings

- Modulating the salen ligand electronics significantly impacts product distribution and catalytic efficiency.
- The complex with para-CF3 substituents outperformed other analogues in various olefin reactions.
- DFT calculations and experimental data support a mechanism involving iron-hydride intermediates and hydrogen atom transfer.

## Abstract

Salen ligands are
privileged scaffolds in transition metal catalysis
due to their electronic tunability and capacity to stabilize diverse
oxidation states. Herein, we report the synthesis and comparative
study of three electronically differentiated [Fe­(salen)]2(μ-oxo) complexes and their application in catalytic reductive
hydroamination (HA) of nitroarenes with alkenes. A mechanistic framework
involving iron-hydride intermediates and hydrogen atom transfer (HAT)
was developed, revealing that modulation of the salen ligand electronics
significantly impacts product distribution and catalytic efficiency.
Systematic investigation of substrate LUMO energies and precatalyst
UV–vis spectroscopy, cyclic voltammetry, along with DFT calculations
on the key HAT step, was undertaken. Notably, the complex bearing para-CF3 substituents outperformed its analogues
across a range of olefin partners. These findings underscore the critical
role of ligand electronics in tuning HAT-based catalysis.