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

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

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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

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

Formation of a Uranium Trithiocarbonate Complex via the Nucleophilic Addition of a Sulfide-Bridged Uranium Complex to CS₂

The uranium­(IV)/uranium­(IV) μ-sulfide complex [{((^AdArO)₃N)­U}₂(μ-S)] reacts with CS₂ to form the trithiocarbonate-bridged complex [{((^AdArO)₃N)­U}₂(μ-κ²:κ²-CS₃)]. The trithiocarbonate complex can alternatively be formed in low yields from low-valent [((^AdArO)₃N)­U­(DME)] through the reductive cleavage of CS₂

Observation of the Inverse Trans Influence (ITI) in a Uranium(V) Imide Coordination Complex: An Experimental Study and Theoretical Evaluation

An inverse trans influence has been observed in a high-valent U­(V) imide complex, [((^AdArO)₃N)­U­(NMes)]. A thorough theoretical evaluation has been employed in order to corroborate the ITI in this unusual complex. Computations on the target complex, [((^AdArO)₃N)­U­(NMes)], and the model complexes [((^MeArO)₃N)­U­(NMes)] and [(NMe₃)­(OMe₂)­(OMe)₃U­(NPh)] are discussed along with synthetic details and supporting spectroscopic data. Additionally, the syntheses and full characterization data of the related U­(V) trimethylsilylimide complex [((^AdArO)₃N)­U­(NTMS)] and U­(IV) azide complex [((^AdArO)₃N)­U­(N₃)] are also presented for comparison