Journal
INORGANIC CHEMISTRY
Volume 49, Issue 21, Pages 10007-10012Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic1013285
Keywords
-
Categories
Funding
- Chemical Sciences, Geosciences, and Biosciences Division
- Office of Basic Energy Sciences of the Department of Energy
- Glenn T. Scaborg Institute at LANL
- National Nuclear Security Administration of the U.S. Department of Energy at Los Alamos National Laboratory [DE-AC5206NA25396]
Ask authors/readers for more resources
The synthesis of a rare trivalent Th3+ complex, (C5Me5)(2)[(PrNC)-Pr-i(Me)(NPr)-Pr-i]Th, initiated a density functional theory analysis on the electronic and molecular structures of trivalent actinide complexes of this type for An = Th, Pa, U, Np, Pu, and Am. While the 6d orbital is found to accommodate the unpaired spin in the Th3+ species, the next member of the series, Pa, is characterized by an f(2) ground state, and later actinides successively fill the 5f shell. In this report, we principally examine the evolution of the bonding as one advances along the actinide row. We find that the early actinides (Pa-Np) are characterized by localized f orbitals and essentially ionic bonding, whereas the f orbitals in the later members of the series (Pu, Am) exhibit significant interaction and spin delocalization into the carbon- and nitrogen-based ligand orbitals. This is perhaps counter-intuitive since the f orbital radius and hence metal-ligand overlap decreases with increasing Z, but this trend is counter-acted by the fact that the actinide contraction also leads to a stabilization of the f orbital manifold that leads to a near degeneracy between the An 5f and cyclopentadienyl pi-orbitals for Pu and Am, causing a significant orbital interaction.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available