CO2 conversion to phenyl isocyanates by uranium(vi) bis(imido) complexes

Leonor Maria; Nuno A G Bandeira; Joaquim Marçalo; Isabel C Santos; John K Gibson

doi:10.1039/c9cc07411b

CO₂ conversion to phenyl isocyanates by uranium(vi) bis(imido) complexes

Chem Commun (Camb). 2020 Jan 2;56(3):431-434. doi: 10.1039/c9cc07411b.

Authors

Leonor Maria¹, Nuno A G Bandeira, Joaquim Marçalo, Isabel C Santos, John K Gibson

Affiliation

¹ Centro de Ciências e Tecnologias Nucleares (C2TN), Instituto Superior Técnico, Universidade de Lisboa, 2695-066 Bobadela, Portugal. leonorm@ctn.tecnico.ulisboa.pt.

PMID: 31825029
DOI: 10.1039/c9cc07411b

Abstract

Uranium(vi) trans-bis(imido) complexes [U(κ4-{(tBu2ArO)2Me2-cyclam})(NPh)(NPhR)] react with CO2 to eliminate phenyl isocyanates and afford uranium(vi) trans-[O[double bond, length as m-dash]U[double bond, length as m-dash]NR]2+ complexes, including [U(κ4-{(tBu2ArO)2Me2-cyclam})(NPh)(O)] that was crystallographically characterized. DFT studies indicate that the reaction proceeds by endergonic formation of a cycloaddition intermediate; the secondary reaction to form a dioxo uranyl complex is both thermodynamically and kinetically hindered.