Revised Bisphenoxide Text.pdf (1.1 MB)
Carbon dioxide activation by a uranium(III) complex derived from a chelating bis(aryloxide) ligand
journal contribution
posted on 2023-06-09, 06:27 authored by Christopher J Inman, Alistair S P Frey, Alexander F R Kilpatrick, Geoff Cloke, S Mark RoeThe new dianionic ligand, C6H4{p-C(CH3)2C6H2Me2O-}2 (= p-Me2bp), featuring two aryloxide donors and a central arene ring, has been synthesized, and used to prepare the mixed-ligand U(III) compound, [U(Cp*)(p-Me2bp)] which exhibits an ?6-interaction with the uranium center. Reductive activation of CO2 was investigated using [U(Cp*)(p-Me2bp)] in supercritical CO2, which gave a dinuclear uranium carbonate complex,{U(Cp*)(p-Me2bp)}2(µ-?1:?2-CO3), cleanly and selectively. Reactivity studies in conventional solvents using lower pressures of CO2 showed the formation of a rare U(IV) oxalate complex, {U(Cp*)(p-Me2bp)}2(µ-?2:?2-C2O2), alongside {U(Cp*)(p-Me2bp)}2(µ-?1:?2-CO3). The relative ratio of the latter two products is temperature dependent: at low temperatures (-78 °C) oxalate formation is favored, whilst at room temperature the carbonate is the dominant product. The U(IV) iodide, [U(Cp*)(p-Me2bp)I], was also synthesized and used as part of an electrochemical study, the results of which showed that [U(Cp*)(p-Me2bp)] has a UIV/UIII redox couple of -2.18 V vs FeCp2+/0 as well as an possible electrochemically accessible UIII/UII reduction process at -2.56 V vs FeCp2+/0.
History
Publication status
- Published
File Version
- Accepted version
Journal
OrganometallicsISSN
0276-7333Publisher
American Chemical SocietyExternal DOI
Issue
23Volume
36Page range
4539-4545Department affiliated with
- Chemistry Publications
Full text available
- Yes
Peer reviewed?
- Yes
Legacy Posted Date
2017-06-01First Open Access (FOA) Date
2018-06-01First Compliant Deposit (FCD) Date
2017-06-01Usage metrics
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