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C–H Bond Addition across a Transient Uranium–Nitrido Moiety and Formation of a Parent Uranium Imido Complex

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journal contribution
posted on 27.07.2018, 00:00 by Kimberly C. Mullane, Ho Ryu, Thibault Cheisson, Lauren N. Grant, Ji Young Park, Brian C. Manor, Patrick J. Carroll, Mu-Hyun Baik, Daniel J. Mindiola, Eric J. Schelter
Uranium complexes in the +3 and +4 oxidation states were prepared using the anionic PN (PN = (N-(2-(diisopropylphosphino)-4-methylphenyl)-2,4,6-trimethylanilide) ligand framework. New complexes include the halide starting materials, (PN)2UIIII (1) and (PN)2UIVCl2 (2), which both yield (PN)2UIV(N3)2 (3) by reaction with NaN3. Compound 3 was reduced with potassium graphite to produce a putative, transient uranium–nitrido moiety that underwent an intramolecular C–H activation to form a rare example of a parent imido complex, [K­(THF)3]­[(PN)­UIV(NH)­[iPr2P­(C6H3Me)­N­(C6H2Me2CH2)]] (4). Calculated reaction energy profiles strongly suggest that a C–H insertion becomes unfavorable when a reductant is present, offering a distinctively different reaction pathway than previously observed for other uranium nitride complexes.