Structure and Bonding Investigation of Plutonium Peroxocarbonate Complexes Using Cerium Surrogates and Electronic Structure Modeling

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• 作者：Lucas E. Sweet ; Jordan F. CorbeyFrédéric Gendron ; Jochen Autschbach ; Bruce K. McNamaraKate L. Ziegelgruber ; Leah M. Arrigo ; Shane M. Peper ; Jon M. Schwantes
• 刊名：Inorganic Chemistry
• 出版年：2017
• 出版时间：January 17, 2017
• 年：2017
• 卷：56
• 期：2
• 页码：791-801
• 全文大小：553K
• ISSN：1520-510X

文摘

Herein, we report the synthesis and structural characterization of K₈[(CO₃)₃Pu]₂(μ-η²-η²-O₂)₂·12H₂O. This is the second Pu-containing addition to the previously studied alkali-metal peroxocarbonate series M₈[(CO₃)₃A]₂(μ-η²-η²-O₂)₂·xH₂O (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-η²-η²-O₂)₂·12H₂O is not isomorphous with its known Ce analogue. However, a new synthetic route to these M₈[(CO₃)₃A]₂(μ-η²-η²-O₂)₂·12H₂O complexes, described below, has produced crystals of Na₈[(CO₃)₃Ce]₂(μ-η²-η²-O₂)₂·12H₂O 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-η²-η²-O₂)₂·xH₂O 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_p–O_p stretch (O_p = 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 O_p–O_p bond distances appear to relate to supermolecular interactions between the neighboring cations.