Origin of Selectivity of a Triazinyl Ligand for Americium(III) over Neodymium(III)

Dan, David; Celis‐Barros, Cristian; White, Frankie D.; Sperling, Joseph M.; Albrecht‐Schmitt, Thomas E.

doi:10.1002/chem.201806070

Title: Origin of Selectivity of a Triazinyl Ligand for Americium(III) over Neodymium(III)

Journal Article · 03 February 2019 · Chemistry - A European Journal

DOI: https://doi.org/10.1002/chem.201806070 · OSTI ID:2349530

Dan, David ^[1]; Celis‐Barros, Cristian ^[2]; White, Frankie D. ^[2]; Sperling, Joseph M. ^[2]; Albrecht‐Schmitt, Thomas E. ^[2]

Florida State University, Tallahassee, FL (United States); Florida State University
Florida State University, Tallahassee, FL (United States)

[M(EtBTP)₃][BPh₄]₃∙3 CH₃CN (M=Nd, Am; EtBTP=2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl)pyridine) have been synthesized from reactions of MCl₃∙n H₂O with EtBTP in acetonitrile followed by anion metathesis. Structural analysis reveals that these compounds contain M³⁺ cations bound by tridentate EtBTP ligands to create a tricapped trigonal prismatic geometry around the metal centers. Collection of high-resolution, single-crystal X-ray diffraction data also allowed reduction in bond lengths esd's, such that a slight contraction of Δ=0.0158(18) Å in the Am-N versus Nd-N bond lengths was observed, even though these cations ostensibly have matching ionic radii. Theoretical evaluation revealed enhanced metal–ligand bonding through back donation in the [Am(EtBTP)₃]³⁺ complex that is absent in [Nd(EtBTP)₃]³⁺.

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Research Organization:: Florida State University, Tallahassee, FL (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0016568

OSTI ID:: 2349530

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 13 Vol. 25; ISSN 0947-6539

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
actinides
americium complexation
charge transport
coordination chemistry
corrosion
defects
geophysics/geochemistry
lanthanides
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materials and chemistry by design
mechanical behavior
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Title: Origin of Selectivity of a Triazinyl Ligand for Americium(III) over Neodymium(III)

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References (38)

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