期刊
CHEMICAL SCIENCE
卷 6, 期 2, 页码 1548-1561出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c4sc03103b
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资金
- German Federal Ministry of Education and Research (BMBF) [02NUK020A, 02NUK020D]
C5-BPP is a highly efficient N-donor ligand for the separation of trivalent actinides, An(III), from trivalent lanthanides, Ln(III). The molecular origin of the selectivity of C5-BPP and many other N-donor ligands of the BTP-type is still not entirely understood. We present here the first NMR studies on C5-BPP Ln(III) and An(III) complexes. C5-BPP is synthesized with 10% N-15 labeling and characterized by NMR and LIFDI-MS methods. N-15 NMR spectroscopy gives a detailed insight into the bonding of C5-BPP with lanthanides and Am(III) as a representative for trivalent actinide cations, revealing significant differences in N-15 chemical shift for coordinating nitrogen atoms compared to Ln(III) complexes. The temperature dependence of NMR chemical shifts observed for the Am(III) complex indicates a weak paramagnetism. This as well as the observed large chemical shift for coordinating nitrogen atoms show that metal-ligand bonding in Am(C5-BPP)(3) has a larger share of covalence than in lanthanide complexes, confirming earlier studies. The Am(C5-BPP)(3) NMR sample is furthermore spiked with Cm(III) and characterized by time-resolved laser fluorescence spectroscopy (TRLFS), yielding important information on the speciation of trace amounts of minor complex species.
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