Uranium(VI) bis(imido) chalcogenate complexes: synthesis and density functional theory analysis

Bis(imido) uranium(VI) trans- and cis-dichalcogenate complexes with the general formula U(N(t)Bu)(2)(EAr)(2)(OPPh(3))(2) (EAr = O-2-(t)BuC(6)H(4), SPh, SePh, TePh) and U(N(t)Bu)(2)(EAr)(2)(R(2)bpy) (EAr = SPh, SePh, TePh) (R(2)bpy = 4,4'-disubstituted-2,2'-bipyridyl, R = Me, (t)Bu) have been prepared. This family of complexes includes the first reported monodentate selenolate and tellurolate complexes of uranium(VI). Density functional theory calculations show that covalent interactions in the U-E bond increase in the trans-dichalcogenate series U(N(t)Bu)(2)(EAr)(2)(OPPh(3))(2) as the size of the chalcogenate donor increases and that both 5f and 6d orbital participation is important in the M-E bonds of U-S, U-Se, and U-Te complexes.