Imido exchange in bis(imido) uranium(VI) complexes with aryl isocyanates

Addition of 1 and 2 equiv of ArNCO (ArPh, 2,4,6-Me3C6H2) to U(NtBu)2(I)2(OPPh3)2 yields the aryl−imido complexes U(NAr)(NtBu)(I)2(OPPh3)2 and U(NAr)2(I)2(OPPh3)2, respectively. Unlike analogous transition metal reactions this imido exchange reaction does not proceed through a metal oxo intermediate. Density functional theory calculations and 15N-labeling studies suggest this transformation involves the [2 + 2] cycloaddition of the aryl isocyanate CN bond across the UN imido ligand to form an N,N-bound ureato intermediate.