Activation of elemental chalcogens has been investigated for transition metals but is mostly unexplored for the actinide elements. The bonding between actinide ions and hard ligands, containing nitrogen or oxygen, is predominantly ionic, whereas bonding interactions with softer, heavier chalcogenide ligands could help to understand M?L covalency in actinide complexes.We recently reported the formation of a U(IV/IV) bridging carbonate complex via U(III)-mediated reductive cleavage of CO2, yielding a �-oxo bridged complex and CO, followed by the insertion of another molecule of CO2. In a similar strategy, we were able to isolate and characterize several mixed carbonate complexes U?CO2E?U, U?CS2E?U, and even U?OC(S)Se?U by reacting bridged chalcogenide complexes U?E?U (E = S, Se) with CO2, CS2, and COS. Some of these chalcogenido mixed-carbonate complexes represent the first of their kind.Bridged chalcogenide complexes U?E?U (E = S, Se) also show remarkable reactivity towards an excess amount of the corresponding elemental chalcogen; thus, forming dinuclear uranium complexes bridged by �-Emn� ligand fragments.

Activation of elemental chalcogens at uranium coordination complexes and their reactivity towards carbon dioxide and related heteroallenes

246th National Meeting (2013)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.