Reactivity of [U(CH2SiMe2NSiMe3)(NR2)2] (R = SiMe3) with elemental chalcogens: towards a better understanding of chalcogen atom transfer in the actinides

Abstract

The reaction of the U(IV) metallacycle, [U(CH₂SiMe₂NSiMe₃)(NR₂)₂] (R = SiMe₃) with the elemental chalcogens, E (E = S, Se, Te) affords the insertion products, [U(ECH₂SiMe₂NSiMe₃)(NR₂)₂], in good yields. All three can transfer the chalcogen atom to [U(NR₂)₃] to give the bridged mono-chalcogenides [U(NR₂)₃](μ-E) (E = S, Se, Te) and regenerate [U(CH₂SiMe₂NSiMe₃)(NR₂)₂]. Additionally, the reaction of [U(Cl)(NR₂)₃] with 2 equiv. of KSCPh₃ affords the di-sulfide, [K(Et₂O)₂][U(S₂)(NR₂)₃].