TY - JOUR
T1 - Structure and bonding investigation of plutonium peroxocarbonate complexes using cerium surrogates and electronic structure modeling
AU - Sweet, Lucas E.
AU - Corbey, Jordan F.
AU - Gendron, Frederic
AU - Autschbach, Jochen
AU - McNamara, Bruce K.
AU - Ziegelgruber, Kate L.
AU - Arrigo, Leah M.
AU - Peper, Shane M.
AU - Schwantes, Jon M.
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/1/17
Y1 - 2017/1/17
N2 - Herein, we report the synthesis and structural characterization of K8 [(CO3)3Pu]2 (μ-η2-η2-O2)212H2O. This is the second Pu-containing addition to the previously studied alkali-metal peroxocarbonate series M8 [(CO3)3A] 2 (μ-η2-η2- 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-η2-η2-O2)212H2O is not isomorphous with its known Ce analogue. However, a new synthetic route to these M8 [(CO3)3A] 2 (μ-η2-η2-O2)212H2O complexes, described below, has produced crystals of Na8 [(CO3)3Ce] 2 (μ-η2-η2-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-η2-η2-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.
AB - Herein, we report the synthesis and structural characterization of K8 [(CO3)3Pu]2 (μ-η2-η2-O2)212H2O. This is the second Pu-containing addition to the previously studied alkali-metal peroxocarbonate series M8 [(CO3)3A] 2 (μ-η2-η2- 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-η2-η2-O2)212H2O is not isomorphous with its known Ce analogue. However, a new synthetic route to these M8 [(CO3)3A] 2 (μ-η2-η2-O2)212H2O complexes, described below, has produced crystals of Na8 [(CO3)3Ce] 2 (μ-η2-η2-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-η2-η2-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.
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U2 - 10.1021/acs.inorgchem.6b02235
DO - 10.1021/acs.inorgchem.6b02235
M3 - Article
C2 - 28033000
AN - SCOPUS:85009737807
SN - 0020-1669
VL - 56
SP - 791
EP - 801
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 2
ER -