Uranium mono(imido) species have been prepared via the oxidation of Cp*U(PDI)(THF) (1-Cp*) and [CpU(PDI)] (1-Cp), where Cp* = η-1,2,3,4,5-pentamethylcyclopentadienide, Cp = 1-(7,7-dimethylbenzyl)cyclopentadienide, PDI = 2,6-[(Mes)N═CMe]CHN, and Mes = 2,4,6-trimethylphenyl, with organoazides. Treating either with NDIPP (DIPP = 2,6-diisopropylphenyl) formed uranium(IV) mono(imido) complexes, CpU(NDIPP)(PDI) (2-Cp) and Cp*U(NDIPP)(PDI) (2-Cp*), featuring reduced [PDI]. The addition of electron-donating 1-azidoadamantane (NAd) to 1-Cp* generated a dimeric product, [Cp*U(NAd)(HPDI)] (3), from radical coupling at the p-pyridine position of the pyridine(diimine) ligand and H-atom abstraction, formed through a monomeric intermediate that was observed in solution but could not be isolated. To support this, Cp*U(Bu-PDI)(THF) (1-Bu), which has a tert-butyl group protecting the para position, was also treated with NAd, and the monomeric product, Cp*U(NAd)(Bu-PDI) (2-Bu), was isolated. All isolated complexes were analyzed spectroscopically and structurally, and the dynamic solution behavior was examined using electronic absorption spectroscopy.
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