Structure and bonding investigation of plutonium peroxocarbonate complexes using cerium surrogates and electronic structure modeling

Lucas E. Sweet, Jordan F. Corbey, Frederic Gendron, Jochen Autschbach, Bruce K. McNamara, Kate L. Ziegelgruber, Leah M. Arrigo, Shane M. Peper, Jon M. Schwantes

Research output: Contribution to journalArticlepeer-review

16 Scopus citations

Abstract

Herein, we report the synthesis and structural characterization of K8 [(CO3)3Pu]2 (μ-η22-O2)212H2O. This is the second Pu-containing addition to the previously studied alkali-metal peroxocarbonate series M8 [(CO3)3A] 2 (μ-η22- O2)2xH2O (M = alkali metal; A = Ce or Pu; x = 8, 10, 12, or 18), for which only the M = Na analogue has been previously reported when A = Pu. The previously reported crystal structure for Na8 [(CO3)3Pu] 2 (μ-η22-O2)212H2O is not isomorphous with its known Ce analogue. However, a new synthetic route to these M8 [(CO3)3A] 2 (μ-η22-O2)212H2O complexes, described below, has produced crystals of Na8 [(CO3)3Ce] 2 (μ-η22-O2)212H2O that are isomorphous with the previously reported Pu analogue. Via this synthetic method, the M = Na, K, Rb, and Cs salts of M8 [(CO3)3Ce] 2 (μ-η22-O2)2xH2O have also been synthesized for a systematic structural comparison with each other and the available Pu analogues using single-crystal X-ray diffraction, Raman spectroscopy, and density functional theory calculations. The Ce salts, in particular, demonstrate subtle differences in the peroxide bond lengths, which correlate with Raman shifts for the peroxide Op-Op stretch (Op = O atoms of the peroxide bridges) with each of the cations studied: Na+ [1.492(3) Å/847 cm-1], Rb+ [1.471(1) Å/854 cm-1], Cs+ [1.474(1) Å/859 cm-1], and K+ [1.468(6) Å/ 870 cm-1]. The trends observed in the Op-Op bond distances appear to relate to supermolecular interactions between the neighboring cations.

Original languageEnglish (US)
Pages (from-to)791-801
Number of pages11
JournalInorganic chemistry
Volume56
Issue number2
DOIs
StatePublished - Jan 17 2017

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint

Dive into the research topics of 'Structure and bonding investigation of plutonium peroxocarbonate complexes using cerium surrogates and electronic structure modeling'. Together they form a unique fingerprint.

Cite this