Mixed sandwich imido complexes of Uranium(V) and Uranium(IV): Synthesis, structure and redox behaviour

Tsoureas, Nikolaos and Cloke, F Geoffrey N (2017) Mixed sandwich imido complexes of Uranium(V) and Uranium(IV): Synthesis, structure and redox behaviour. Journal of Organometallic Chemistry. ISSN 0022-328X

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Abstract

The mixed sandwich U(III) complex {U[η ^8 -C8H6(1,4-Si( iPr)3)2](Cp*)(THF)} reacts with the organic azides RN3 (R = SiMe3, 1-Ad, BMes2) to afford the corresponding, structurally characterised U(V) imido complexes {U[η ^8 -C8H6(1,4-Si( iPr)3)2](Cp*)(NR)}. In the case of R=SiMe3, the reducing power of the U(III) complex leads to reductive coupling as a parallel minor reaction pathway, forming R-R and the U(IV) azide-bridged complex{[U]}2(µ-N3)2, along with the expected [U]=NR complex. All three [U] =NR complexes show a quasi-reversible one electron reduction between -1.6 to -1.75 V, and for R= SiMe3, chemical reduction using K/Hg affords the anionic U(IV) complex K+ {U[η ^8 -C8H6(1,4-Si( iPr)3)2](Cp*)=NSiMe3} - . The molecular structure of the latter shows an extended structure in the solid state in which the K counter cations are successively sandwiched between the Cp* ligand of one [U] anion and the COTtips2 ligand of the next.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Subjects: Q Science > QD Chemistry > QD0146 Inorganic chemistry
Depositing User: Geoff Cloke
Date Deposited: 13 Sep 2017 11:15
Last Modified: 27 Sep 2017 14:29
URI: http://sro.sussex.ac.uk/id/eprint/70182

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