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].
![Graphical abstract: Reactivity of [U(CH2SiMe2NSiMe3)(NR2)2] (R = SiMe3) with elemental chalcogens: towards a better understanding of chalcogen atom transfer in the actinides](http://hg.y866.cn/compound/lib/scimg/usr/1/C5NJ00739A.jpg)