Abstract
AbstractThermolysis of the nitride‐bridged diuranium(IV) complex Cs{(μ‐N)[U(OSi(OtBu)3)3]2} (1) showed that the bridging nitride behaves as a strong nucleophile, promoting N−C bond formation by siloxide ligand fragmentation to yield an imido‐bridged siloxide/silanediolate diuranium(IV) complex, Cs{(μ‐NtBu)(μ‐O2Si(OtBu)2)U2(OSi(OtBu)3)5}. Complex 1 displayed reactivity towards CS2 and CO2 at room temperature that is unprecedented in f‐element chemistry, affording diverse N‐functionalized products depending on the reaction stoichiometry. The reaction of 1 with two equivalents of CS2 yielded the thiocyanate/thiocarbonate complex Cs{(μ‐NCS)(μ‐CS3)[U(OSi(OtBu)3)3]2} via a putative NCS−/S2− intermediate. The reaction of 1 with one equivalent of CO2 resulted in deoxygenation and N−C bond formation, yielding the cyanate/oxo complex Cs{(μ‐NCO)(μ‐O)[U(OSi(OtBu)3)3]2}. Addition of excess CO2 to 1 led to the unprecedented dicarbamate product Cs{(μ‐NC2O4)[U(OSi(OtBu)3)3]2}.
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