A Uranium(VI)-Oxo-Imido Dimer Complex Derived from a Sterically Demanding Triamidoamine

Philip Cobb, Ashley Wooles, Stephen Liddle

Research output: Contribution to journalArticlepeer-review

Abstract

Reaction of [UO2(µ-Cl)4{K(18-crown-6)}2] with [{N(CH2CH2NSiPri 3)3}Li3] gives [{UO(µNCH2CH2N[CH2CH2NSiPri 3]2)}2] (1), [{(LiCl)(KCl)(18-crown-6)}2] (2), and [LiOSiPri 3] (3) in a 1:2:2 ratio. The formation of the oxo-imido 1 involves cleavage of a N-Si bond, and activation of one of the usually robust U=O bonds of uranyl(VI), resulting in formation of uranium(VI)-imido and siloxide linkages. Notably, the uranium oxidation state remains unchanged at +6 in starting material and product. Structural characterization suggests the dominance of a core RN=U=O group, and the dimeric formulation of 1 is supported by bridging imido linkages in a highly asymmetric U2N2 ring. DFT analysis finds s > p orbital energy ordering for the U=N and U=O bonds in 1, which is uranyllike in nature. Complexes 1-3 were characterized variously by single crystal X-ray diffraction, multinuclear NMR, IR, Raman, and optical spectroscopies, cyclic voltammetry, and density functional theory.
Original languageEnglish
JournalInorganic Chemistry
Publication statusAccepted/In press - 15 Jun 2020

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