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Structure and Bonding Investigation of Plutonium Peroxocarbonate Complexes Using Cerium Surrogates and Electronic Structure Modeling
21
Citations
52
References
2016
Year
Herein, we report the synthesis and structural characterization of K<sub>8</sub>[(CO<sub>3</sub>)<sub>3</sub>Pu]<sub>2</sub>(μ-η<sup>2</sup>-η<sup>2</sup>-O<sub>2</sub>)<sub>2</sub>·12H<sub>2</sub>O. This is the second Pu-containing addition to the previously studied alkali-metal peroxocarbonate series M<sub>8</sub>[(CO<sub>3</sub>)<sub>3</sub>A]<sub>2</sub>(μ-η<sup>2</sup>-η<sup>2</sup>-O<sub>2</sub>)<sub>2</sub>·xH<sub>2</sub>O (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 Na<sub>8</sub>[(CO<sub>3</sub>)<sub>3</sub>Pu]<sub>2</sub>(μ-η<sup>2</sup>-η<sup>2</sup>-O<sub>2</sub>)<sub>2</sub>·12H<sub>2</sub>O is not isomorphous with its known Ce analogue. However, a new synthetic route to these M<sub>8</sub>[(CO<sub>3</sub>)<sub>3</sub>A]<sub>2</sub>(μ-η<sup>2</sup>-η<sup>2</sup>-O<sub>2</sub>)<sub>2</sub>·12H<sub>2</sub>O complexes, described below, has produced crystals of Na<sub>8</sub>[(CO<sub>3</sub>)<sub>3</sub>Ce]<sub>2</sub>(μ-η<sup>2</sup>-η<sup>2</sup>-O<sub>2</sub>)<sub>2</sub>·12H<sub>2</sub>O that are isomorphous with the previously reported Pu analogue. Via this synthetic method, the M = Na, K, Rb, and Cs salts of M<sub>8</sub>[(CO<sub>3</sub>)<sub>3</sub>Ce]<sub>2</sub>(μ-η<sup>2</sup>-η<sup>2</sup>-O<sub>2</sub>)<sub>2</sub>·xH<sub>2</sub>O 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 O<sub>p</sub>-O<sub>p</sub> stretch (O<sub>p</sub> = O atoms of the peroxide bridges) with each of the cations studied: Na<sup>+</sup> [1.492(3) Å/847 cm<sup>-1</sup>], Rb<sup>+</sup> [1.471(1) Å/854 cm<sup>-1</sup>], Cs<sup>+</sup> [1.474(1) Å/859 cm<sup>-1</sup>], and K<sup>+</sup> [1.468(6) Å/870 cm<sup>-1</sup>]. The trends observed in the O<sub>p</sub>-O<sub>p</sub> bond distances appear to relate to supermolecular interactions between the neighboring cations.
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