Experimental and Quantum Mechanical Characterization of an Oxygen-Bridged Plutonium(IV) Dimer

Debmalya Ray, Jing Xie, Jacob White, Ginger E. Sigmon, Laura Gagliardi, Amy E. Hixon

Research output: Contribution to journalArticlepeer-review

9 Scopus citations


We report the synthesis and characterization of K4{[PuCl2(NO3)3]22-O)}⋅H2O, which contains the first known μ2-oxo bridge between two PuIV metal centers. Adding to its uniqueness is the Pu−(μ2-O) bond length of 2.04 Å, which is the shortest of other analogous compounds. The Pu−(μ2-O)−Pu bridge is characterized by the mixing of s-, d-, and p-orbitals from Pu with the p-orbitals of O; the 5f-orbitals do not participate in bonding. Natural bond orbital analysis indicates that Pu and O interact through one 3c-2e σPu-O-Pu and two 3c-2e πPu-O-Pu bonding orbitals and that the electron density is highly polarized on the μ2-O. Bond topology properties analysis indicates that the Pu−(μ2-O) bond shares both ionic and covalent character. Quantum mechanical calculations also show that the dimer has multiconfigurational ground states, where the nonet, septet, quintet, triplet, and singlet are close in energy. This work demonstrates the interplay between experimental and computational efforts that is required to understand the chemical bonding of Pu compounds.

Original languageEnglish (US)
Pages (from-to)8115-8120
Number of pages6
JournalChemistry - A European Journal
Issue number36
StatePublished - Jun 26 2020

Bibliographical note

Funding Information:
This work was supported by the National Nuclear Security Administration, Department of Energy, under Award Number DE‐NA0003763.

Publisher Copyright:
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


  • O-ligands
  • actinides
  • density functional calculations
  • electronic structure
  • plutonium


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