Thorium- and uranium-azide reductions: a transient dithorium-nitride versus isolable diuranium-nitrides - INSA Toulouse - Institut National des Sciences Appliquées de Toulouse Access content directly
Journal Articles Chemical Science Year : 2019

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

Abstract

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(CH2CH2NSiMe2But)(3)}(3-)) with NaN3 or KN3, respectively, affords very rare examples of actinide molecular square and triangle complexes [{M(Tren(DMBS))(mu-N-3)}(n)] (M = U, n = 4, 3; Th, n = 3, 4). Chemical reduction of 3 produces [{U(Tren(DMBS))}(2)(mu-N)][K(THF)(6)] (5) and [{U(Tren(DMBS))}(2)(mu-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)(mu-NH)] (7) or [{Th(Tren(DMBS))}{Th(N[CH2CH2NSiMe2But](2)CH2CH2NSi[mu-CH2]MeBut)}(mu-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 sigma > pi 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.
Fichier principal
Vignette du fichier
c8sc05473h.pdf (1.04 Mo) Télécharger le fichier
Origin Publication funded by an institution

Dates and versions

hal-04022188 , version 1 (20-12-2023)

Licence

Identifiers

Cite

Jingzhen Du, David M. King, Lucile Chatelain, Erli Lu, Floriana Tuna, et al.. Thorium- and uranium-azide reductions: a transient dithorium-nitride versus isolable diuranium-nitrides. Chemical Science, 2019, 10 (13), pp.3738-3745. ⟨10.1039/c8sc05473h⟩. ⟨hal-04022188⟩
10 View
5 Download

Altmetric

Share

Gmail Mastodon Facebook X LinkedIn More