Imido JOMC Evans special issue Revised.pdf (1.07 MB)
Mixed sandwich imido complexes of Uranium(V) and Uranium(IV): Synthesis, structure and redox behaviour
journal contribution
posted on 2023-06-09, 07:53 authored by Nikolaos Tsoureas, Geoff ClokeThe mixed sandwich U(III) complex {U[? ^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[? ^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[? ^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.
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- Published
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- Accepted version
Journal
Journal of Organometallic ChemistryISSN
0022-328XPublisher
ElsevierExternal DOI
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857Page range
25-53Department affiliated with
- Chemistry Publications
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- Yes
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- Yes
Legacy Posted Date
2017-09-13First Open Access (FOA) Date
2018-09-04First Compliant Deposit (FCD) Date
2017-09-13Usage metrics
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