# Comparative Nitrene-Transfer Chemistry to Olefins Mediated by First-Row Transition Metal Catalysts Supported by a Pyridinophane Macrocycle with N4 Ligation

## TL;DR

This study explores how different transition metals supported by a specific ligand affect the efficiency of nitrene transfer to olefins, focusing on copper's superior performance.

## Contribution

The paper introduces a new ligand-supported first-row transition metal system for nitrene transfer and reveals distinct mechanistic pathways for Cu(I) and Cu(II).

## Key findings

- Copper(I) and Copper(II) reagents show high efficacy in aziridination of para-substituted styrenes.
- Copper reagents form two N–C bonds sequentially during aziridination, with distinct mechanistic parameters.
- Computed electrophilicity of Cu(I)-derived nitrene correlates with its faster catalytic activity.

## Abstract

A 12-membered pyridinophane scaffold containing two pyridine and two tertiary amine residues is examined as a prototype ligand (tBuN4) for supporting nitrene transfer to olefins. The known [(tBuN4)MII(MeCN)2]2+ (M = Mn, Fe, Co, and Ni) and [(tBuN4)CuI(MeCN)]+ cations are synthesized with the hexafluorophosphate counteranion. The aziridination of para-substituted styrenes with PhI=NTs (Ts = tosyl) in various solvents proved to be high yielding for the Cu(I) and Cu(II) reagents, in contrast to the modest efficacy of all other metals. For α-substituted styrenes, aziridination is accompanied by products of aziridine ring opening, especially in chlorinated solvents. Bulkier β-substituted styrenes reduce product yields, largely for the Cu(II) reagent. Aromatic olefins are more reactive than aliphatic congeners by a significant margin. Mechanistic studies (Hammett plots, KIE, and stereochemical scrambling) suggest that both copper reagents operate via sequential formation of two N–C bonds during the aziridination of styrene, but with differential mechanistic parameters, pointing towards two distinct catalytic manifolds. Computational studies indicate that the putative copper nitrenes derived from Cu(I) and Cu(II) are each associated with closely spaced dual spin states, featuring high spin densities on the nitrene N atom. The computed electrophilicity of the Cu(I)-derived nitrene reflects the faster operation of the Cu(I) manifold.