一氢化硼
| 一氢化硼 | |
|---|---|
| |
| IUPAC名 λ1-borane | |
| 识别 | |
| CAS号 | 13766-26-2 
|
| PubChem | 6397184 11094539 58594784 |
| ChemSpider | 4910333 |
| SMILES |
|
| InChI |
|
| InChIKey | UWBOAQKPEXKXSU-UHFFFAOYSA-N |
| Gmelin | 33 |
| ChEBI | 38983 |
| 性质 | |
| 化学式 | HB |
| 摩尔质量 | 11.82 g·mol−1 |
| 热力学[1] | |
| ΔfHm⦵298K | 442.7 |
| S⦵298K | 172 |
| 若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。 | |
一氢化硼，又称硼烷(1)或甲硼烯，是一种不稳定的硼的氢化物，化学式 BH。
产生
一氢化硼可以由紫外线照射羰基甲硼烷而成。
- BH3CO → BH + CH2O[2]
当硼化合物在氢气存在下被加热到高温时，就会形成一氢化硼。[3]
硼阴离子B− 和氢阳离子 H+反应也会形成一氢化硼。它也可以由硼原子和氢气反应而成。
- B + H2 → BH + H
BH2 的反应能量太大，不稳定。[4]
一氢化硼可能存在于太阳黑子中，[5]不过直到 2008年仍未被检测到。[6]
性质
一氢化硼的电离能为 9.77 eV。[7]在基态下，它的键解离能为 81.5 kcal/mol。[8]一氢化硼的电子亲和能为 0.3 eV，形成 HB−离子。[9]
在基态下，一氢化硼的偶极矩是 1.27 德拜，第一激发态 A1Π 的一氢化硼则为 0.58 德拜。[10]
尽管 BH 是闭壳分子，但它是顺磁性，这与温度无关。[11]
反应
大量的一氢化硼并不稳定，在 20 托的气压下，会在 20 ns 的时间迅速消失。[12] 一氢化硼会和氧气反应，产物可能是 HBO。[2]一氢化硼不和甲烷反应，但它会和丙烷反应，形成 C3H7BH2。它和一氧化氮反应，可能产生 HBO 和HBNO。一氢化硼会和双键加成，也会和水反应。[2]
一氢化硼可以以聚一氢化硼固体的形式出现，它在空气中会自燃。[13]
一氢化硼在50 GPa时，预测会形成空间群Ibam 的固体，在超过 168 GPa时，会形成空间群为 P6/mmm的金属态。[14]
相关离子
一氢化硼阳离子和双阳离子都是已知的。双阳离子 HB2+ 可以由有两个键的 σ配体框架支撑。[15]一氢化硼双阴离子可以由胺稳定化。[16]
参考资料
- ^ GROMACS Molecule Database - boron-monohydride. virtualchemistry.org. [2021-07-10]. （原始内容存档于2021-07-10）.
- ^ 2.0 2.1 2.2 Garland, Nancy L.; Stanton, C. T.; Fleming, James W.; Baronavski, A. P.; Nelson, H. H. Boron monohydride reaction kinetics studied with a high-temperature reactor. The Journal of Physical Chemistry. June 1990, 94 (12): 4952–4956. doi:10.1021/j100375a036.
- ^ Abad, Carlos; Florek, Stefan; Becker-Ross, Helmut; Huang, Mao-Dong; Heinrich, Hans-Joachim; Recknagel, Sebastian; Vogl, Jochen; Jakubowski, Norbert; Panne, Ulrich. Determination of boron isotope ratios by high-resolution continuum source molecular absorption spectrometry using graphite furnace vaporizers. Spectrochimica Acta Part B: Atomic Spectroscopy. October 2017, 136: 116–122. Bibcode:2017AcSpe.136..116A. doi:10.1016/j.sab.2017.08.012.
- ^ Yang, Xuefeng; Dagdigian, Paul J. Chemiluminescence spectra and cross sections for the reaction of boron(4p 2P) with hydrogen and deuterium. The Journal of Physical Chemistry. 1993, 97 (17): 4270–4276. ISSN 0022-3654. doi:10.1021/j100119a006 （英语）.
- ^ Engvold, O. The diatomic molecules BH, BN, and BO in sunspots and the solar abundance of boron. Solar Physics. February 1970, 11 (2): 183–197. Bibcode:1970SoPh...11..183E. S2CID 119720128. doi:10.1007/BF00155219.
- ^ Karthikeyan, B; Bagare, S; Rajamanickam, N; Raja, V. On the search for BF, BH and BS molecular lines in sunspot spectra. Astroparticle Physics. February 2009, 31 (1): 6–12. Bibcode:2009APh....31....6K. doi:10.1016/j.astropartphys.2008.10.009.
- ^ Haynes, William M. CRC Handbook of Chemistry and Physics, 93rd Edition. CRC Press. 2012: 10–200 [2021-07-10]. ISBN 9781439880494. （原始内容存档于2021-07-10） （英语）.
- ^ Bauschlicher, Charles W.; Langhoff, Stephen R.; Taylor, Peter R. On the dissociation energy of BH. The Journal of Chemical Physics. July 1990, 93 (1): 502–506. Bibcode:1990JChPh..93..502B. doi:10.1063/1.459550.
- ^ Reid, C.J. Electron affinities of BH, B2, BC and BN molecules determined using charge inversion spectrometry. International Journal of Mass Spectrometry and Ion Processes. August 1993, 127: 147–160. Bibcode:1993IJMSI.127..147R. doi:10.1016/0168-1176(93)87087-9.
- ^ Thomson, Ritchie; Dalby, F. W. An experimental determination of the dipole moments of the X ( 1 Σ) and A ( 1 Π) states of the BH molecule. Canadian Journal of Physics. June 1969, 47 (11): 1155–1158. Bibcode:1969CaJPh..47.1155T. doi:10.1139/p69-144.
- ^ Fowler, P.W.; Steiner, E. Paramagnetic closed-shell molecules: the isoelectronic series CH + , BH and BeH -. Molecular Physics. 20 December 1991, 74 (6): 1147–1158. Bibcode:1991MolPh..74.1147F. doi:10.1080/00268979100102871.
- ^ Bauer, S. H. Oxidation of B, BH, BH3, and BmHn Species: Thermochemistry and Kinetics. Chemical Reviews. January 1996, 96 (6): 1907–1916. PMID 11848815. doi:10.1021/cr941034q.
- ^ Urben, Peter. Bretherick's Handbook of Reactive Chemical Hazards. Elsevier. 2013: 71 [2021-07-10]. ISBN 9780080523408. （原始内容存档于2021-07-10） （英语）.
- ^ Hu, Chao-Hao; Oganov, Artem R.; Zhu, Qiang; Qian, Guang-Rui; Frapper, Gilles; Lyakhov, Andriy O.; Zhou, Huai-Ying. Pressure-Induced Stabilization and Insulator-Superconductor Transition of BH. Physical Review Letters. 19 April 2013, 110 (16): 165504. Bibcode:2013PhRvL.110p5504H. PMID 23679618. doi:10.1103/PhysRevLett.110.165504
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- ^ Chen, Wen-Ching; Lee, Ching-Yu; Lin, Bo-Chao; Hsu, Yu-Chen; Shen, Jiun-Shian; Hsu, Chao-Ping; Yap, Glenn P. A.; Ong, Tiow-Gan. The Elusive Three-Coordinate Dicationic Hydrido Boron Complex. Journal of the American Chemical Society. 10 January 2014, 136 (3): 914–917. PMID 24383448. doi:10.1021/ja4120852.
- ^ Vargas-Baca, Ignacio; Findlater, Michael; Powell, Adam; Vasudevan, Kalyan V.; Cowley, Alan H. Boron di- and tri-cations. Dalton Transactions. 2008, (45): 6421–6. PMID 19002329. doi:10.1039/b810575h.
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