Compound 2

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Compound data: 1H NMR

Compound data: 31P NMR

Compound data: 13C NMR

Compound data: 7Li NMR

Compound data: Raman

Compound data: FTIR

Compound data: Crystallographic data

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

Method A: At ambient temperature and under nitrogen atmosphere, a solution of 1-azidoadamantane in benzene (59.7 mg, 0.337 mmol, 2 ml) was added to a stirring suspension of 1 in benzene (500 mg, 0.337 mmol, 3 ml). Immediate effervescence was observed along with dissolution of 1. The black mixture was allowed to stir at ambient temperature for 1 hour. All volatiles were removed under vacuum. The residue was extracted with toluene (3 × 2 ml); the volume was concentrated to approximately 3 ml and kept under −35 °C. After 12 hours the first crop of 2 was collected as blackish red crystals. The mother liquor was further concentrated to approximately 2 ml and was kept under −35 °C for 12 hours to produce the second crop of 2. The blackish red crystals from the two crops were combined, washed with pentane (3 × 1 ml) under −35 °C, and dried under vacuum to afford 2 as a blackish red crystalline solid. Yield: 143.4 mg, 28%. Method B: The procedure was carried out in an identical manner to Method A, but the reaction was carried out under argon atmosphere. Complex 2 was produced as 2 crops of blackish red crystals. Yield: 132.2 mg, 26%. Single crystals of 2 suitable for X-ray diffraction were obtained from a mixture of toluene/benzene solution at −35 °C. Anal. Calcd for C₆₉H₁₀₄N₈O₆P₂Si₂ULi·(C₆H₆)₂: C, 59.02; H, 7.16; N, 6.63%. Found: C, 59.77; H, 7.17; N, 5.59.% ¹H NMR (C₆D₆, 298 K): δ 8.24 (m, 7 H, ArH), 7.25 (m, 8 H, ArH), 7.19 (m, 4 H, ArH), 7.12 (m, 5 H, ArH), 7.07-7.01 (m, 8 H, ArH), 3.44 (br, 10 H, OCH₂ or NCH₂), 3.26 (br, 12 H, OCH₂ or NCH₂), 2.22 (br, 10 H, OCH₂, NCH₂ or C-H of 1-adamantyl), 2.11 (s, 6 H, OCH₂, NCH₂ or C-H of 1-adamantyl), 2.09 (br, 6 H, OCH₂, NCH₂ or C-H of 1-adamantyl), 1.41 (m, br, 10 H, OCH₂, NCH₂ or C-H of 1-adamantyl), 1.34 (s, br, 10 H, OCH₂, NCH₂ or C-H of 1-adamantyl), 0.76 (s, 18 H, -SiMe₃). ³¹P{¹H} NMR (C₆D₆, 298 K): δ −17.91 (s). ¹³C{¹H} NMR (C₆D₆, 298 K): δ 145.15, 137.49, 132.50, 128.93, 125.29 (ArC), 99.98 (U=C), 73.14, 68.90, 68.05, 54.59, 53.58, 36.64, 31.37, 21.04 (NC/CH/CH₂ of 1-adamantyl or CH₂ of 2, 2, 2-cryptand), 3.91 (-SiMe₃). ⁷Li{¹H} NMR (C₆D₆, 298 K): δ −1.31 (s, br). The ²⁹Si NMR spectrum did not exhibit any resonances, which is attributed to the low solubility of 2 in benzene once isolated in crystalline form combined with the unfavourable −γ NMR property of the ²⁹Si nucleus. Evans Method (C₆D6, 298 K): 2.28 μ_B. Attenuated total reflectance infrared (ν cm^–1: 3050 (w), 2898 (s), 2843 (s), 1976 (m), 1495 (m), 1449 (m), 1433 (s), 1368 (s), 1299 (s), 1237 (s), 1104 (m), 1078 (m), 1027 (w), 1017 (w), 982 (s), 959 (s), 945 (m), 928 (m), 830 (m), 798 (w), 749 (m), 729 (m), 710 (s), 694 (s), 675 (s), 657 (s), 633 (s), 616 (s), 601 (s), 520 (s), 509 (s), 484 (s), 466 (s), 420 (s). Raman ν/cm^-1 (Neat, ≤ 5 mW): 3057 (m), 2891 (br, w), 1941 (br, w), 1586 (s), 1100 (br, m), 1285 (br, w), 629 (s). It should be noted that due to the sensitivity of the complex, any irradiating laser with power of > 1.5 mW causes visually observable signs of decomposition. On the other hand, multiple accumulation/long exposure time using reduced power laser are not available either, due to the thermal instability of the complex at room temperature, as well as due to its air/moisture sensitivity in the Raman cell. Attempts at dispersing 2 to suppress decomposition were unsuccessful.