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 [{(((Ad)ArO)(3)N)U}(2)(μ-η(1):κ(2)-CO(3))] via reductive cleavage of CO(2), yielding a μ-oxo bridged complex, followed by the insertion of another molecule of CO(2). In a similar strategy, we were able to isolate and characterize a series of mixed carbonate complexes U-CO(2)E-U, U-CS(2)E-U, and even U-OC(S)Se-U, by reacting bridged chalcogenide complexes [{(((Ad)ArO)(3)N)U}(2)(μ-E)] (E = S, Se) with CO(2), CS(2), and COS. These chalcogenido mixed-carbonate complexes represent the first of their kind.