Metal-metal bonding in molecular actinide compounds: electronic structure of [M2X8](2-) (M = U, Np, Pu; X = Cl, Br, I) complexes and comparison with d-block analogues

Density functional and multiconfigurational ( ab initio) calculations have been performed on [M2X8](2-) (X = Cl, Br, I) complexes of 4d (Mo, Tc, Ru), 5d (W, Re, Os), and 5f (U, Np, Pu) metals in order to investigate general trends, similarities and differences in the electronic structure and metal-metal bonding between f-block and d-block elements. Multiple metal-metal bonds consisting of a combination of sigma and pi interactions have been found in all species investigated, with delta-like interactions also occurring in the complexes of Tc, Re, Np, Ru, Os, and Pu. The molecular orbital analysis indicates that these metal-metal interactions possess predominantly d(z2) (sigma), d(xz) and d(yz) (pi), or d(xy) and d(x2-y2) (delta) character in the d-block species, and f(z3) (sigma), f(z2x) and f(z2y) (pi), or f(xyz) and f(z) (delta) character in the actinide systems. In the latter, all three (sigma, pi, delta) types of interaction exhibit bonding character, irrespective of whether the molecular symmetry is D-4h or D-4d. By contrast, although the nature and properties of the sigma and p bonds are largely similar for the D-4h and D-4d forms of the d-block complexes, the two most relevant metal-metal delta-like orbitals occur as a bonding and antibonding combination in D-4h symmetry but as a nonbonding level in D-4d symmetry. Multiconfigurational calculations have been performed on a subset of the actinide complexes, and show that a single electronic configuration plays a dominant role and corresponds to the lowest-energy configuration obtained using density functional theory.