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[en] Novel cis- and trans-bis(imido) uranium di-sulfonamide derivatives have been prepared from iodide metathesis reactions between two equivalents of K[N(Me)(SO2Ar')] (Ar' = 4-Me-C6H4) and U(NtBu)2(I)2(L)x (L = OPPh3, x=2; Me2bpy, x=1; Me2bpy=4,4'-dimethyl-2,2'-bi-pyridyl). These bis(amide) derivatives serve as useful precursors for the synthesis of the trans-di-phenolate complex U(NtBu)2(O-2-tBuC6H4)2(OPPh3)2 (5), cis- and trans-di-thiolate complexes U(NtBu)2(SPh)2(L)x (L=OPPh3 (6); Me2bpy (7)), and cis- and trans-di-halide complexes with the general formulas U(NtBu)2(X)2(L)x (X=Cl, L=OPPh3 (8), L=Me2bpy (10); X=Br, LOPPh3 (9), L=Me2bpy (11)). DFT calculations performed on the trans-di-halide series U(NtBu)2(X)2(L)2 and the UO22+ analogues UO2X2(OPPh3)2 suggest that the uranium centers in the [U(NtBu)2]2+ ions possess more covalent character than analogous UO22+ derivatives but that the U-X bonds in the U(NtBu)2X2L2 complexes possess a more ionic nature. (authors)
Journal
Comptes Rendus. Chimie; ISSN 1631-0748; 
; (no.6-7t.13); p. 758-766
; (no.6-7t.13); p. 758-766