十二氫合十二硼酸根

十二氫合十二硼酸根
別名	Dodecahydrododecaborate(2-)
識別
CAS號	12356-13-7
SMILES	[BH-]1234[BH]5%12%13[BH]1%10%11[BH]289[BH]367[BH]145[BH]6%14%15[BH]78%16[BH]9%10%17[BH]%11%12%18[BH]1%13%14[BH-]%15%16%17%18;
Gmelin	3407
ChEBI	33594
性質
化學式	H12B12
摩爾質量	141.83 g·mol−1
相關物質
相關化學品	銫鹽：十二氫合十二硼酸銫
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

十二氫合十二硼酸根，化學式 [B₁₂H₁₂]²⁻，有着正二十面體結構，每個硼原子都連接一個氫原子。

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製備和反應

十二氫合十二硼酸根 [B₁₂H₁₂]²⁻的存在性最早由 H. C. Longuet-Higgins 和M. de V. Roberts 在1955年預測。^[1]五年後，Hawthorne 和Pitochelli 首次通過2-碘癸硼烷和三乙胺在80 °C的苯溶液中的反應，首次得到十二氫合十二硼酸鹽。^[2]更方便的製備方法可通過硼氫化鈉的兩步製備而成。首先，使用三氟化硼的乙醚加合物將硼氫化物轉化為八氫合三硼酸鹽：

5 NaBH₄ + BF₃ → 2 NaB₃H₈ + 3 NaF + 2 H₂

之後熱解八氫合三硼酸鹽，可以得到十二氫合十二硼酸鈉。^[3]其它合成方法也被發表了。

十二氫合十二硼酸鹽在空氣中穩定，不與熱氫氧化鈉和鹽酸反應。十二氫合十二硼酸根可以被電氧化成 [B₂₄H₂₃]³⁻。^[4]

B
12H2−
12被過氧化氫羥基化，可以得到 [B₁₂(OH)₁₂]²⁻。^[5]

潛在應用

基於 [B₁₂H₁₂]²⁻ 離子的化合物用於放射性離子¹⁵²Eu³⁺ 和²⁴¹Am³⁺的溶劑提取已評估。^[6]

[B₁₂H₁₂]²⁻、[B₁₂(OH)₁₂]²⁻ 和[B₁₂(OMe)₁₂]²⁻ 可用於藥物釋放（英語：drug delivery）。它們會形成籠式結構，已被用於製造非靶向的高性能MRI造影劑（英語：MRI contrast agent），並在腫瘤組織中持久存在。^[7]

[B₁₂H₁₂]²⁻ 的鹽是癌症治療中的潛在治療劑。對於中子捕獲治療中的應用，十二氫合十二硼酸鹽的衍生物增加了中子輻照治療的特異性。中子輻射會導致硼-10在腫瘤附近發射α粒子。^[8]

參考資料

[1]
Longuet-Higgins, Hugh Christopher; Roberts, M. de V. The electronic structure of an icosahedron of boron atoms. Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences. June 1955, 230 (1180): 110–119. Bibcode:1955RSPSA.230..110L. S2CID 98533477. doi:10.1098/rspa.1955.0115.
[2]
Pitochelli, Anthony R.; Hawthorne, Frederick M. The Isolation of Icosahedral B
12H2−
12 Ion. Journal of the American Chemical Society. June 1960, 82 (12): 3228–3229. doi:10.1021/ja01497a069.
[3]
Miller, H. C.; Muetterties, E. L.; Boone, J. L.; Garrett, P.; Hawthorne, M. F. Borane Anions. Inorganic Syntheses. 2007: 81–91. ISBN 978-0-470-13241-8. doi:10.1002/9780470132418.ch16.
[4]
Sivaev, Igor B.; Bregadze, Vladimir I.; Sjöberg, Stefan. Chemistry of closo-Dodecaborate Anion [B₁₂H₁₂]²⁻: A Review. Collection of Czechoslovak Chemical Communications. 2002, 67 (6): 679–727. doi:10.1135/cccc20020679.
[5]
Rauchfuss, Thomas B. (編). Boron Cluster Compounds. Inorganic Syntheses. 2010: 56–66. ISBN 978-0-470-65156-8. doi:10.1002/9780470651568.ch2.
[6]
Bernard, R.; Cornu, D.; Grüner, B.; Dozol, J.-F.; Miele, P.; Bonnetot, B. Synthesis of [B₁₂H₁₂]^2– based extractants and their application for the treatment of nuclear wastes. Journal of Organometallic Chemistry. September 2002, 657 (1–2): 83–90. doi:10.1016/S0022-328X(02)01540-1.
[7]
Axtell, J. C. Synthesis and Applications of Perfunctionalized Boron Clusters. Inorganic Chemistry. 2018, 57 (5): 2333–2350. PMC 5985200 . PMID 29465227. doi:10.1021/acs.inorgchem.7b02912.
[8]
Tachikawa, S.; Miyoshi, T.; Koganei, H.; El-Zaria, M.E.; Vinas, C.; Suzuki, M.; Ono, K.; Nakamura, H. Spermidinium closo-dodecaborate-encapsulating liposomes as efficient boron delivery vehicles for neutron capture therapy. Chemical Communications. 2014, 50 (82): 12325–12328. PMID 25182569. doi:10.1039/c4cc04344h .

[1] [1]
Longuet-Higgins, Hugh Christopher; Roberts, M. de V. The electronic structure of an icosahedron of boron atoms. Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences. June 1955, 230 (1180): 110–119. Bibcode:1955RSPSA.230..110L. S2CID 98533477. doi:10.1098/rspa.1955.0115.

[2] [2]
Pitochelli, Anthony R.; Hawthorne, Frederick M. The Isolation of Icosahedral B
12H2−
12 Ion. Journal of the American Chemical Society. June 1960, 82 (12): 3228–3229. doi:10.1021/ja01497a069.

[3] [3]
Miller, H. C.; Muetterties, E. L.; Boone, J. L.; Garrett, P.; Hawthorne, M. F. Borane Anions. Inorganic Syntheses. 2007: 81–91. ISBN 978-0-470-13241-8. doi:10.1002/9780470132418.ch16.

[Sivaeva002-4] [4]
Sivaev, Igor B.; Bregadze, Vladimir I.; Sjöberg, Stefan. Chemistry of closo-Dodecaborate Anion [B₁₂H₁₂]²⁻: A Review. Collection of Czechoslovak Chemical Communications. 2002, 67 (6): 679–727. doi:10.1135/cccc20020679.

[5] [5]
Rauchfuss, Thomas B. (編). Boron Cluster Compounds. Inorganic Syntheses. 2010: 56–66. ISBN 978-0-470-65156-8. doi:10.1002/9780470651568.ch2.

[6] [6]
Bernard, R.; Cornu, D.; Grüner, B.; Dozol, J.-F.; Miele, P.; Bonnetot, B. Synthesis of [B₁₂H₁₂]^2– based extractants and their application for the treatment of nuclear wastes. Journal of Organometallic Chemistry. September 2002, 657 (1–2): 83–90. doi:10.1016/S0022-328X(02)01540-1.

[[10]-7] [7]
Axtell, J. C. Synthesis and Applications of Perfunctionalized Boron Clusters. Inorganic Chemistry. 2018, 57 (5): 2333–2350. PMC 5985200 . PMID 29465227. doi:10.1021/acs.inorgchem.7b02912.

[8] [8]
Tachikawa, S.; Miyoshi, T.; Koganei, H.; El-Zaria, M.E.; Vinas, C.; Suzuki, M.; Ono, K.; Nakamura, H. Spermidinium closo-dodecaborate-encapsulating liposomes as efficient boron delivery vehicles for neutron capture therapy. Chemical Communications. 2014, 50 (82): 12325–12328. PMID 25182569. doi:10.1039/c4cc04344h .

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