Non–linear bonding trends in maleonitrile-1,2–dithiolate complexes of the transuranium actinides (An3+ = Np3+ – Cf3+ excl. Bk3+)

A series of complexes of the trivalent actinides Np(III) through Cf(III) (excluding Bk(III)) with maleonitrile-1,2-dithiolate (mnt ^2– ) is synthesized along with their lanthanide counterparts (La(III) – Nd(III), Sm(III) – Gd(III), Dy(III)), in order to characterize the nature of chemical bonds with these metal ions and a polarizable non-innocent, sulfur-donor ligand. The metal-sulfur bonds in these complexes trend shorter than measured for lanthanides with equivalent ionic radii; however, particularly large deviations are observed in the neptunium and plutonium complexes in both structure and bonding, resulting in a nonlinear bond length trendline for the actinide series. Density Functional Theory (DFT) calculations with Quantum Theory of Atoms in Molecules (QTAIM) and Natural Bond Order (NBO) analyses indicate that for the neptunium and plutonium complexes, the presence of increased 5 f -orbital participation, energy degeneracy of the metal and ligand orbitals, and the structure packing result in shortened M–S bonds. The stabilization of the energy of the 5 f -orbitals and the decrease in f -contribution to bonding orbitals in the later actinides results in structural properties more similar to the lanthanide complexes.