34074-95-8Relevant articles and documents
Carbon Dioxide Activation by a Uranium(III) Complex Derived from a Chelating Bis(aryloxide) Ligand
Inman, Christopher J.,Frey, Alistair S. P.,Kilpatrick, Alexander F.R.,Cloke, F. Geoffrey N.,Roe, S. Mark
, p. 4539 - 4545 (2017)
The 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 η6 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-η1:η2-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-η2:η2-C2O2), alongside {U(Cp?)(p-Me2bp)}2(μ-η1:η2-CO3). The relative ratio of the last two products is temperature dependent: at low temperatures (-78 °C) oxalate formation is favored, while 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 a possible electrochemically accessible UIII/UII reduction process at -2.56 V vs FeCp2+/0.