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四羰基钴酸

四羰基合钴(-I)酸
别名 四羰基氢化钴
四羰基合钴(-1)酸
识别
CAS号 16842-03-8  checkY=
PubChem 61848
SMILES
 
  • O=C=[CoH](=C=O)(=C=O)=C=O
性质
化学式 C4HCoO4
摩尔质量 171.98 g·mol⁻¹
外观 浅黄色液体
氣味 恶臭[1]
熔点 -33 °C(240 K)
沸点 47 °C(320 K)
溶解性 0.05% (20°C)[1]
溶解性 可溶于己烷甲苯乙醇
蒸氣壓 >1 atm (20°C)[1]
pKa 1(水中)[2]
8.3(乙腈中)[3]
危险性
主要危害 可燃,在空气中分解[1]
PEL [1]
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。

四羰基钴酸(又称四羰基氢化钴四羰基合钴(-I)酸)是一种金属有机化合物,化学式为HCo(CO)4。它是挥发性的黄色液体,其蒸气无色,具有恶臭。[4]它在空气中易被氧化,微溶于水,是一种强酸。[5]

制备

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四羰基合钴(-I)酸最早被Hieber在20世纪30年代初期描述。[6]它是第二个被发现的过渡金属形成的氢化物。它可由Co2(CO)8和钠汞齐或其它还原剂反应,酸化后得到:[7]

Co2(CO)8 + 2 Na → 2 NaCo(CO)4
NaCo(CO)4 + H+ → HCo(CO)4 + Na+

由于HCo(CO)4能够迅速分解,它也能通过Co2(CO)8的原位加氢得到:[8]

Co2(CO)8 + H2 ⇌ 2 HCo(CO)4

平衡反应的热力学参数由红外光谱确定ΔH = 4.054 kcal mol−1, ΔS = −3.067 cal mol−1 K−1[8]

参考文献

[编辑]
  1. ^ 1.0 1.1 1.2 1.3 1.4 NIOSH Pocket Guide to Chemical Hazards. #0148. NIOSH. 
  2. ^ Holleman, Arnold F.; Wiberg, Egon; Wiberg, Nils. Lehrbuch der anorganischen Chemie. Berlin. 1995. ISBN 978-3-11-012641-9. OCLC 237142268 (德语). 
  3. ^ Moore, Eric J.; Sullivan, Jeffrey M.; Norton, Jack R. Kinetic and thermodynamic acidity of hydrido transition-metal complexes. 3. Thermodynamic acidity of common mononuclear carbonyl hydrides. Journal of the American Chemical Society (American Chemical Society (ACS)). 1986, 108 (9): 2257–2263. ISSN 0002-7863. doi:10.1021/ja00269a022. 
  4. ^ Kerr, W. J. Sodium Tetracarbonylcobaltate. Encyclopedia of Reagents for Organic Synthesis. 2001. doi:10.1002/047084289X.rs105. 
  5. ^ 无机化学丛书 第九卷 锰分族 铁系 铂系. 北京:科学出版社. pp 289. 钴的羰基氢化物
  6. ^ Hieber, W.; Mühlbauer, F.; Ehmann, E. A. Derivate des Kobalt- und Nickelcarbonyls (XVI. Mitteil. über Metallcarbonyle). Berichte der deutschen chemischen Gesellschaft (A and B Series). 1932, 65 (7): 1090. doi:10.1002/cber.19320650709. 
  7. ^ Donaldson, J. D.; Beyersmann, D. Cobalt and Cobalt Compounds. Ullmann's Encyclopedia of Industrial Chemistry. Wiley-VCH. 2005. doi:10.1002/14356007.a07_281.pub2. 
  8. ^ 8.0 8.1 Pfeffer, M.; Grellier, M. Cobalt Organometallics. Comprehensive Organometallic Chemistry III. Elsevier. 2007. doi:10.1016/B0-08-045047-4/00096-0. 
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四羰基钴酸
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