Compound 4
6,6',6''-((1,4,7-triazacyclononane-1,4,7-triyl)tris(methylene))tris(2-(adamantan-1-yl)-4-methylphenolate)uranium(V) oxide
From: The role of uranium–arene bonding in H2O reduction catalysis
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Compound data: CIF
Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.
A solution of [((Ad,MeArO)3tacn)U] (25 mg, 2.22 · 10–5 mol) in THF (5 mL) was treated with H2O (0.1M in THF, 233 µL, 2.33 · 10–5 mol) and stirred for 3 days until the reaction mixture turned blue-green. Then, the solvent was removed in vacuo. After re-dissolving in toluene (2 mL), 2.2.2 cryptand (9.0 mg, 2.40 · 10–5 mol) and potassium bis(trimethylsilyl)amide (4.8 mg, 2.40 · 10–5 mol) were added to the mixture as solutions in toluene (1 mL). After complete addition, the solvent was removed immediately to yield a yellow powder that was redissolved in THF (2 mL) and treated with a solution of ferrocenium BArF20 (18.8 mg, 2.17 · 10–5 mol) in THF (1 mL) and stirred for 5 min. The solvent was removed in vacuo and the orange solid triturated with pentane (3 x 1 mL). The solid was suspended in pentane, collected on a frit and washed with pentane (3 x 2 mL). The product was then washed through the frit with benzene (into a new vial) and dried in vacuo to yield the title compound as an orange powder. Single crystals suitable for XRD analysis were obtained from diffusion of Si(CH3)4 in a DME solution at –35 °C. Yield: 83% (21.0 mg, 1.84 10–5 mol) 1H NMR (400 MHz, benzene-d6, RT) δH = –26.14 (br. s., 3H), –5.49 (d., J = 7.4 Hz, 9 H), 0.50 (br. s., 9 H), 1.86 (br. s., 3 H), 1.91 (br. s., 9 H), 1.97 (s., 9 H), 1.99 (s., 9 H), 2.49 (br. s., 9 H), 2.52 (br. s., 3 H), 3.01 (s., 3 H), 3.90 (s., 3 H), 15.81 (br. s., 3 H), 16.43 (br. s., 3 H), 28.21 (br. s., 3 H) ppm. Elemental Analysis for C60H78N3O4U · Si(CH3)4: Calculated: C, 62.42; H, 7.37; N, 3.41; Found: C, 62.75; H, 7.81; N, 2.90. IR: ν [cm–1] = 2901 (vs), 2847 (s), 1512 (m), 1462 (vs), 1358 (m), 1257 (vs), 1155 (m), 1134 (m), 1105 (vs), 1032 (m), 980 (m), 951 (m), 862 (w), 827 (m), 810 (m), 777 (m), 756 (w), 638 (m), 573 (w), 519 (m), 443 (w), 419 (s).
