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Molecular uranium-nitrides are now well known, but there are no isolable molecular thorium-nitrides outside of cryogenic matrix isolation experiments. We report that treatment of [M(Tren DMBS )(I)] (M = U, 1 ; Th, 2 ; Tren DMBS = {N(CH 2 CH 2 NSiMe 2 Bu  t  ) 3 } 3- ) with NaN 3 or KN 3 , respectively, affords very rare examples of actinide molecular square and triangle complexes [{M(Tren DMBS )(μ-N 3 )}  n  ] (M = U, n = 4, 3 ; Th, n = 3, 4 ). Chemical reduction of 3 produces [{U(Tren DMBS )} 2 (μ-N)][K(THF) 6 ] ( 5 ) and [{U(Tren DMBS )} 2 (μ-N)] ( 6 ), whereas photolysis produces exclusively 6 . Complexes 5 and 6 can be reversibly inter-converted by oxidation and reduction, respectively, showing that these UNU cores are robust with no evidence for any C-H bond activations being observed. In contrast, reductions of 4 in arene or ethereal solvents gives [{Th(Tren DMBS )} 2 (μ-NH)] ( 7 ) or [{Th(Tren DMBS )}{Th(N[CH 2 CH 2 NSiMe 2 Bu  t  ] 2 CH 2 CH 2 NSi[μ-CH 2 ]MeBu  t  )}(μ-NH)][K(DME) 4 ] ( 8 ), respectively, providing evidence unprecedented outside of matrix isolation for a transient dithorium-nitride. This suggests that thorium-nitrides are intrinsically much more reactive than uranium-nitrides, since they consistently activate C-H bonds to form rare examples of Th-N(H)-Th linkages with alkyl by-products. The conversion here of a bridging thorium(iv)-nitride to imido-alkyl combination by 1,2-addition parallels the reactivity of transient terminal uranium(iv)-nitrides, but contrasts to terminal uranium(vi)-nitrides that produce alkyl-amides by 1,1-insertion, suggesting a systematic general pattern of C-H activation chemistry for metal(iv)- vs. metal(vi)-nitrides. Surprisingly, computational studies reveal a σ &gt; π energy ordering for all these bridging nitride bonds, a phenomenon for actinides only observed before in terminal uranium nitrides and uranyl with very short U-N or U-O distances.

Thorium- and uranium-azide reductions: a transient dithorium-nitride versus isolable diuranium-nitrides