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一氢化硼

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一氢化硼
IUPAC名
λ1-borane
识别
CAS号 13766-26-2  checkY
PubChem 6397184
11094539
58594784
ChemSpider 4910333
SMILES
 
  • [BH]
InChI
 
  • 1S/BH/h1H
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]
ΔfHm298K 442.7
S298K 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)甲硼烯,是一种不稳定的氢化物,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 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

  1. ^ GROMACS Molecule Database - boron-monohydride. virtualchemistry.org. [2021-07-10]. (原始内容存档于2021-07-10). 
  2. ^ 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. 
  3. ^ 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. 
  4. ^ 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). 
  5. ^ 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. 
  6. ^ 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. 
  7. ^ 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). 
  8. ^ 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. 
  9. ^ 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. 
  10. ^ 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. 
  11. ^ 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. 
  12. ^ 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. 
  13. ^ 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). 
  14. ^ 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可免费查阅. 
  15. ^ 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. 
  16. ^ 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.