Reactivity of U–E–U (E = S, Se) Toward CO₂, CS₂, and COS: New Mixed-Carbonate Complexes of the Types U–CO₂E–U (E = S, Se), U–CS₂E–U (E = O, Se), and U–COSSe–U

We recently reported the formation of a bridging carbonate complex [{((AdArO)3N)­U}2(μ–η1:κ2-CO3)] via reductive cleavage of CO2, yielding a μ-oxo bridged complex, followed by the insertion of another molecule of CO2. In a similar strategy, we were able to isolate and characterize a series of mixed carbonate complexes U–CO2E–U, U–CS2E–U, and even U–OC­(S)­Se–U, by reacting bridged chalcogenide complexes [{((AdArO)3N)­U}2(μ-E)] (E = S, Se) with CO2, CS2, and COS. These chalcogenido mixed-carbonate complexes represent the first of their kind.