# Facile N–C bond cleavage and arene reduction by a transient uranium(ii) complex

## TL;DR

A rare uranium(II) complex enables unique chemical reactions like N–C bond cleavage and arene reduction.

## Contribution

Discovery of a highly reactive uranium(II) intermediate and its solvent-dependent reactivity.

## Key findings

- Uranium(II) complex enables intramolecular N–C bond cleavage.
- Formation of an inverse-sandwich complex and a putative U–N2 complex in different solvents.
- Electronic structure of the inverse-sandwich complex is an equilibrium between two states.

## Abstract

Complexes of uranium(ii) remain extremely rare and their reactivity is practically unexplored. Here we report that the reduction of the heteroleptic bis-aryloxide U(iii) complex [U(κ6-{(tBu2ArO)2Me2-cyclam})I], A, yields a rare and highly reactive U(ii) intermediate that enables a rare example of intramolecular uranium mediated N–C cleavage and effects arene reduction resulting in the isolation of the U(iv) complex [U{κ5-((tBu2ArO)Me2-cyclam)}{κ2-(tBu2ArOCH2)}] (2) and of the inverse–sandwich complex [{U(κ5-{(tBu2ArO)2Me2-cyclam})}2(μ-η6:η6-benzene)] (3) respectively. Moreover, the U(ii) solvent-dependent reactivity results in the formation of a putative U–N2 complex in diethyl ether. Computational, EPR and magnetic studies indicate the electronic structure of 3 to be an equilibrium between two possible electronic structures very close in energy: (U(iv)–arene4−–U(iv) and U(iii)–arene2−–U(iii)). These results indicate that polydentate amine-phenolate ligands can be used to access highly reactive U(ii) intermediates and that provides evidence that U(ii) species are involved in the formation of inverse sandwich complexes.

A highly reactive U(ii) intermediate supported by a polydentate amine-phenolate ligand undergoes solvent dependent divergent reactivity affording an inverse–sandwich complex in benzene, N–C cleavage in THF and N2 activation in diethyl ether.