On the Origin of Covalent Bonding in Heavy Actinides.

Recent reports have suggested the late actinides participate in more covalent interactions than the earlier actinides, yet the origin of this shift in chemistry is not understood. This report considers the chemistry of actinide dipicolinate complexes to identify why covalent interactions become more prominent for heavy actinides. A modest increase in measured actinide:dipicolinate stability constants is coincident with a significant increase in An 5f energy degeneracy with the dipicolinate molecular orbitals for Bk and Cf relative to Am and Cm. While the interactions in the actinide-dipicolinate complex are largely ionic, the decrease in 5f orbital energy across the series manifests in orbital-mixing and, hence, covalency driven by energy degeneracy. This observation suggests the origin of covalency in heavy actinide interactions stems from the degeneracy of 5f orbitals with ligand molecular orbitals rather than spatial orbital overlap. These findings suggest that the limiting radial extension of the 5f orbitals later in the actinide series could make the heavy actinides ideal elements to probe and tune effects of energy degeneracy driven covalency.

Characterization of berkelium(III) dipicolinate and borate compounds in solution and the solid state.

Berkelium is positioned at a crucial location in the actinide series between the inherently stable half-filled 5f(7) configuration of curium and the abrupt transition in chemical behavior created by the onset of a metastable divalent state that starts at californium. However, the mere 320-day half-life of berkelium's only available isotope, (249)Bk, has hindered in-depth studies of the element's coordination chemistry. Herein, we report the synthesis and detailed solid-state and solution-phase characterization of a berkelium coordination complex, Bk(III)tris(dipicolinate), as well as a chemically distinct Bk(III) borate material for comparison. We demonstrate that berkelium's complexation is analogous to that of californium. However, from a range of spectroscopic techniques and quantum mechanical calculations, it is clear that spin-orbit coupling contributes significantly to berkelium's multiconfigurational ground state.