Synthesis of Novel BTPhen-Functionalized Silica-Coated Magnetic Nanoparticles for Separating Trivalent Actinides and Lanthanides

Dedicated to Victor Snieckus, a valued friend and colleague, on the occasion of his 80^th birthday

Abstract

Bis-(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) functionalized magnetic nanoparticles (MNPs), which selectively extract Am(III) over europium(III) from 0.1 M HNO₃ with fast kinetics and a separation factor of 30 have been synthesized. These MNPs also show a small but significant selectivity for Am(III) over Cm(III) with a separation factor of around 3 in 0.1 M HNO₃. We report also the synthesis of these BTPhen and related ligands via an improved synthetic route bypassing the problematic benzylic oxidation with stoichiometric SeO₂.

Key words

spent nuclear fuel - BTPhen ligand - magnetic nanoparticles - solid-phase extraction - benzylic halogenation

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• 38 Synthesis of BTPhen 10 To a suspension of 1,10-phenanthroline-2,9-dicarbohydrazon­amide (8, 0.60 g, 2 mmol) in THF (100 mL) and MeOH (100 mL) was added 4,4′-dihydroxybenzil (9, 1.10 g, 4.6 mmol, 2.3 equiv). Et₃N (50 mL, 356.2 mmol) was added, and the mixture was heated at 81 °C for 3 d. The solution was allowed to cool to r.t., filtered, and the remaining solid residue washed with CH₂Cl₂ (25 mL). The filtrate was evaporated, and the solid was triturated with MeOH (100 mL). The insoluble solid was filtered, washed with further MeOH (50 mL) and Et₂O (50 mL), and allowed to dry in air to afford the ligand 10 as a yellow solid (0.99 g, 69%); mp 280–282 °C (decomposed). ¹H NMR (400 MHz, DMSO-d ₆): δ = 6.78–6.93 (m, 8 H), 7.51–7.71 (m, 8 H), 8.11 (s, 2 H), 8.58 (d, J = 8.0 Hz, 2 H), 8.61 (d, J = 8.0 Hz, 2 H). ¹³C NMR (101 MHz, DMSO-d ₆): δ = 115.4, 122.9, 125.5, 126.1, 127.7, 129.5, 130.7, 131.6, 137.7, 145.5, 152.6, 154.6, 155.3, 159.0, 159.6, 160.5. FTMS + P ESI: m/z calcd for C₄₂H₂₇O₄N₈ [M + H]⁺: 707.2150; found: 707.2153. IR: ν_max = 3206, 1608, 1590, 1483, 1442 cm^–1.