Understanding structure and bonding in early actinide 6d(0)5f0 MX6q (M = Th-Np; X = H, F) complexes in comparison with their transition metal 5d0 analogues.

The relationship between structure and bonding in actinide 6d(0)5f(0) MX(6)(q)() complexes (M = Th, Pa, U, Np; X = H, F; q = -2,-1, 0, +1) has been studied, based on density functional calculations with accurate relativistic actinide pseudopotentials. The detailed comparison of these prototype systems with their 5d(0) transition metal analogues (M = Hf, Ta, W, Re) reveals in detail how the 5f orbitals modify the structural preferences of the actinide complexes relative to the transition metal systems. Natural bond orbital analyses on the hydride complexes indicate that 5f orbital involvement in sigma-bonding favors classical structures based on the octahedron, while d orbital contributions to sigma-bonding favor symmetry lowering. The respective roles of f and d orbitals are reversed in the case of pi-bonding, as shown for the fluoride complexes.