Organometallics
Organometallics
5 years ago

Carbon Dioxide Activation by a Uranium(III) Complex Derived from a Chelating Bis(aryloxide) Ligand

Carbon Dioxide Activation by a Uranium(III) Complex Derived from a Chelating Bis(aryloxide) Ligand
Alistair S. P. Frey, S. Mark Roe, Alexander F. R. Kilpatrick, F. Geoffrey N. Cloke, Christopher J. Inman
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.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00263

DOI: 10.1021/acs.organomet.7b00263

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.