Origin of Selectivity of a Triazinyl Ligand for Americium(III) over Neodymium(III) |
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| Authors: | David Dan Dr Cristian Celis-Barros Dr Frankie D White Joseph M Sperling Prof Dr Thomas E Albrecht-Schmitt |
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| Institution: | Department of Chemistry and Biochemistry, Florida State University, Tallahasse, Florida, 32306 USA |
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| Abstract: | 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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| Keywords: | actinides americium complexation coordination chemistry lanthanides neodymium complexation |
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