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Theoretical Study of Divalent Bis(Pentaisopropylcyclopentadienyl) Actinocenes

preprint
submitted on 17.08.2019 and posted on 19.08.2019 by Jason M. Yu, Filipp Furche
The existence of divalent bis(pentaisopropylcyclopentadienyl) actinocene compounds, An(CpiPr5)2 for An = (Th, U, Pu, Am, Bk, No, Lr), is assessed by density functional theory (DFT) calculations with scalar-relativistic small core pseudopotentials. The calculations predict ground states with significant 6d occupation for Th, U, and Lr, whereas Am, Bk, and No exhibit 5f ground states. A mixed ground state with predominant 5f character is found for Pu. The complexes exhibit a linear coordination geometry and high S10 symmetry except for Pu(CpiPr5)2 and Am(CpiPr5)2, which are found to be bent by 11 and 12 degrees , respectively. Absorption spectra are simulated with time-dependent density functional theory (TD-DFT) and compared to experimental spectra of known tris(C4H4SiMe3) and tris(C5H3(SiMe3)2) compounds [M. E. Fieser et al., J. Am. Chem. Soc. 2015, 137, 369-382] as well as recently synthesized divalent lanthanide analogs Dy(CpiPr5)2 and Tb(CpiPr5)2 [C. Gould et al., J. Am. Chem. Soc. 2019, accepted]. Thermodynamic stability is assessed by calculation of adiabatic reduction potentials of the trivalent precursors [An(CpiPr5 )2] +, and the feasibility of further reduction to obtain as yet unknown monovalent molecular actinide complexes is discussed.

Funding

NSF grant CHE1800431

History

Email Address of Submitting Author

yujm1@uci.edu

Institution

University of California, Irvine

Country

United States

ORCID For Submitting Author

0000-0002-2270-6798

Declaration of Conflict of Interest

Principal investigator Filipp Furche has an equity interest in Turbomole GmbH. The terms of this arrangement have been reviewed and approved by the University of California, Irvine, in accordance with its conflict of interest policies.

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