Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 139, Issue 29, Pages 9901-9908Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b03251
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Funding
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Elements Chemistry Program at Colorado School of Mines [DE-SC0012039]
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Elements Chemistry Program at Los Alamos National Laboratory
- National Nuclear Security Administration of U.S. Department of Energy [DE-AC52-06NA25396]
- U.S. DOE BER
- U.S. Department of Energy (DOE) [DE-SC0012039] Funding Source: U.S. Department of Energy (DOE)
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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.
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