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Crystals 2022, 12, 1339 3 of 7 potassium and sodium salts of the [CB11H12]− anion. This method avoids the exchange of cation, significantly simplifies the reaction procedure and can be easily scaled-up. 2. Materials and Methods 2.1. Starting Materials All manipulations were carried out on a Schlenk line or in a glovebox filled with high- purity nitrogen. Dry THF and DME were obtained by distillation from Na/benzophenone. K[B11H14] and Na[B11H14] were purchased from ZhengzhouYuanli technology. Potassium hydride, (trifluoromethyl)trimethylsilane, sodium hydride, sodium bis(trimethylsilyl)amide, tetrahydrofuran, 1,2-dimethoxyethane, DMSO-d6 (D, 98%) were purchased from Energy Chemicals, Aladdin, Heowns or Royaltech. The 1H and 1H{11B} NMR spectra were obtained using a Bruker Advance NEO 400 MHz instrument from Germany. The 13C NMR spectra were recorded at 101 Hz. The 11B, 11B{1H} and 11B-11B cosy NMR spectra were recorded at 128 MHz. All 11B chemical shifts were referenced to BF3·OEt2 in C6D6 (0.0 ppm), with a negative sign indicating an upfield shift. All 1H chemical shifts were measured relative to internal residual hydrogens from the lock solvents (98% DMSO-d6). 2.2. Synthesis of Na[CB11H12] Na[B11H14] (1.58 g, 10 mmol), NaH (0.72 g, 30 mmol) and NaHMDS (1.84 g, 10 mmol) were added to a 100 mL Schlenk flask, which was equipped with a reflux condenser. The flask was connected with a Schlenk line and 40 mL 1,2-dimethoxyethane was injected. The reaction mixture was stirred under 0 ◦C for 15 min and (trifluoromethyl)trimethylsilane (4 mL, 30 mmol) was added. Then, the mixture was stirred at 60 ◦C for 3 days and a large amount of yellow precipitate was generated. After cooling down to room temperature and quenched with water (1 mL). The residue was subjected to extractive workup with ether (4 × 60 mL) and H2O (4 × 60 mL). The organic phases were combined, and the solvent was evaporated to give a yellow oily product. Then, 1,4-dioxane was added into the oil residue until a large amount of white solid precipitate. The precipitate was filtered and then dried under dynamic vacuum to produce a 1,4-dioxane solvated Na[CB11H12] white powder. Solvent free Na[CB11H12] (1.14 g, 68% yield) was obtained by dissolving in 20 mL water and drying it first in a rotary evaporator and then under dynamic vacuum at 100 ◦C for 2 h. 11B NMR (128 MHz, DMSO-d6) δ −6.95 (d, J = 140.0 Hz, 1B), −13.27 (d, J = 136.3 Hz, 5B), −16.15 (d, J = 150.6 Hz, 5B). 11B{1H} NMR (128 MHz, DMSO-d6) δ −7.01 (1B), −13.27 (5B), −16.16 (5B). 1H NMR (400 MHz, DMSO-d6) δ 2.36 (s, 1H), 2.24–0.70 (m, 11H). 1H{11B} NMR (400 MHz, DMSO-d6) δ 2.36 (s, 1H), 1.55 (s, 6H), 1.40 (s, 5H). 13C{1H} NMR (101 MHz, DMSO-d6) δ 50.65 (s). 2.3. Synthesis of K[CB11H12] K[B11H14] (1.74 g, 10 mmol) and KH (1.20 g, 30 mmol) were added to a 100 mL Schlenk flask. The flask was connected with a Schlenk line and 40 mL of tetrahydrofuran was injected. The reaction mixture was stirred under 0 ◦C for 15 min and then (trifluo- romethyl)trimethylsilane (4 mL, 30 mmol) was added. The Schlenk flask was equipped with a reflux condenser. The mixture was stirred at 60 ◦C for 3 days and a large amount of yellow precipitate was generated. After cooling down to room temperature and quenched with water (1 mL), the residue was subjected to extractive workup with ether (4 × 60 mL) and H2O (4 × 60 mL). The organic phases were combined, and the solvent was removed under reduced pressure to give a yellow oily product. Then, 1,4-dioxane was added into the filtrate until a large amount of white solid precipitate. The precipitate was filtered and then dried under dynamic vacuum to produce 1,4-dioxane solvated K[CB11H12] white powder. The precipitate was washed with dichloromethane (3 × 30 mL) and hexane (3 × 30 mL), and then dried under dynamic vacuum to produce an unsolvated K[CB11H12], white pow- der (1.21 g, 66% yield). 11B NMR (128 MHz, DMSO-d6) δ −6.95 (d, J = 140.0 Hz, 1B), −13.27 (d, J = 136.3 Hz, 5B), −16.15 (d, J = 150.6 Hz, 5B). 11B{1H} NMR (128 MHz, DMSO-d6) δ −7.01 (s), −13.27 (s), −16.16 (s). 1H NMR (400 MHz, DMSO-d6) δ 2.36 (s, 1H), 2.24–0.70 (m,PDF Image | Efficient Way to Directly Synthesize Unsolvated Alkali Metal
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