Leonor Maria, Nuno Bandeira, Joaquim Marçalo, Isabel Cordeiro Santos, and John K Gibson

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=U=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 kinetically hindered.

Doi: 10.1039/C9CC07411B

Cited as: L. Maria, N. Bandeira, J. Marçalo, I. C. Santos and J. K. Gibson, Chem. Commun., 2019; doi: 10.1039/C9CC07411B.