Compound 3

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Compound data: CIF

Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.

A 25-mL Schlenk tube was charged with [(L^Ar)NpCl], 1, (43.2 mg, 0.060 mmol) and 8 mL of dme. An excess of NaK₃ alloy (0.24 mL, eutectic) was added and the suspension was orbital shaken (2800 rpm) for 20 s. During this time the reddish solid was consumed and the colour of the solution changed to brown and later to intense purple black. The excess of the NaK alloy and any particulate matter were removed by syringe filtration (silylated glass fibre membrane in PE housing, 1.0 μm porosity) and the solution of [(L^Ar)Np(dme)] (3a) analysed for direct Vis-nIR measurements (340 μL load into 1.00 mm cell) and crystallization studies (7.4 mL). On two occasions, small black plate-shaped crystals that had grown in the product solution were analysed by X-ray diffraction, but only weakly diffracted and the crystals showed signs of considerable surface degradation so further analysis was not possible. Slow vapour diffusion of n;-pentane into the isolated purple-black solution that were changing color to red-brown with time yielded reddish brown crystals, suitable for single-crystal X‑ray diffraction analysis that are characterised as [K(dme)(L^Ar‑H)Np(OMe)]₂, 3. The crystals were collected, washed with n‑pentane (4 × 1 mL) and dried under vacuum (20 °C, <5×10^-3 mbar, 1 h); isolated yield: 16.1 mg, 34.4%. ATR-IR: ν = 3088 vw, 3068 vw, 3054 vw, 3034 vw, 3013 vw, 2963 w/m, 2928 w/m, 2895 w, 2866 w/m, 2821 w, 2792 w, 1579 w, 1547 vw, 1523 vw, 1485 w, 1471 w, 1450 w/m, 1429 w, 1418 w, 1379 w, 1365 w, 1353 w, 1347 w, 1283 w, 1271 w, 1242 w/m, 1215 w/m, 1195 w, 1180 w, 1158 w/m, 1150 w/m, 1130 w/m, 1118 w/m, 1092 m/s, 1043 s, 1034 s, 1008 m/s, 990 w, 984 w, 964 w/m, 939 w, 917 w, 901 w, 857 m, 796 m, 773 s, 750 m, 734 m, 723 m, 714 m, 685 w/m, 646 w/m, 633 w, 614 w, 570 m, 554 w, 530 m, 488 w/m, 473 w/m, 428 w/m, 400 m, 380 m/s cm^-1. Vis-nIR: (dme, 293 K): λ_max / nm (ε / dm³ mol^-1 cm^-1) = 1349 (329), 1345 (330), 1335 (328), 1300 (291), 1024 (490), 963 (566), 892 (730), 859 (796), 852 (829), 846 (850), 841 (847), 823 (913), 779 (1170). Radiological regulations prohibit combustion-based analysis of the C, H and N content of 3.