Structural/electronic properties and reaction energies of a series of mono- and bis-uranyl dihalides equatorially coordinated by N/O ligands.

Monometallic (UO2)(X)2(L)3 (L = pyridine (py), X = F (1), Cl (2), Br (3) and I (4); L = tetrahydrofuran (thf), X = Cl (5); L = pyrrole (pl), X = Cl (6)) as well as bimetallic [(UO2)(μ2-X)(X)(L)2]2 (L = py, X = F (7), Cl (8), Br (9) and I (10); L = thf, X = Cl (11); L = pl, X = Cl (12); μ 2 = doubly bridged) were examined using relativistic density functional theory. With changing from F, Cl, Br to I irregardless of in mono- or bis-uranyl complexes, bond lengths of U = O were calculated to be decreasing, resulting from strengthening of axial U = O bonds while weakening equatorial X → U coordination. This is further evidenced by calculated bond orders of U = O and stretching vibrational frequencies. A similar situation was is found in 2, 5 and 6 as well as in 8, 11 and 12, where N/O ligands are varied but the chlorine atoms are retained. The present study reveals that all these complexes have U(f)-character low-lying unoccupied orbitals, and their π*(U = O) antibonds are located on higher-energy orbitals. Complex 1 was calculated to show σ(U = O) bonding character for HOMO, and pyridine-character for other occupied orbitals; the fluorine ligand occurs in a relatively low-energy region. In contrast, the π(p) characters of heavier halogen atoms significantly contribute to most frontier molecular orbitals of 2, 3 and 4. Unlike this electronic feature of 2, complexes 5 and 6 exhibit mainly thf and pyrrole characters, respectively, for their high-lying occupied orbitals. Electronic structures of bisuranyl complexes 7-12, albeit a little more complicated, are revealed to be similar to those of the corresponding monouranyl complexes. Finally, energies of formation reactions of the above complexes were calculated and compared with available experimental results.