钴化合物

钴化合物和其它元素形成的化合物。钴在化合物中,最稳定的价态是+2价,在特定配体的存在下,也有+3价的稳定化合物。此外,还存在着高氧化态+4、+5和低氧化态-1、0、+1的钴化合物。

无机化合物

卤化物

红紫色的CoCl2·6H2O

钴(II)的四种卤化物都是已知的,氟化钴(CoF2)是粉色固体,氯化钴(CoCl2)是蓝色固体,溴化钴(CoBr2)是绿色固体,碘化钴(CoI2)是蓝黑色固体。这几种卤化钴除了无水物外,还存在水合物。无水氯化钴是蓝色的,而六水合物是红紫色的。[1]根据氯化钴不同水合状态时的颜色变化,可以用于制造变色硅胶

无水卤化钴在70~120°C和NO反应,生成[Co(NO)2X]2(X=Cl,Br和I)。卤化钴和三乙基膦((C2H5)3P)的配合物在苯中可以吸收NO,生成反磁性的Co(NO)X2(P(C2H5)3)[2]

反应Co3+
+ eCo2+
的电势为+1.92 V,比Cl2Cl(+1.36 V)的要高。因此,Co3+与Cl的作用会产生Co2+并放出氯气。F2F的电势高达+2.87 V,三氟化钴(CoF3)可以稳定存在。它是一种氟化试剂,并且可以和水剧烈反应。[3]

氧化物和氢氧化物

钴可以形成多种氧化物,如CoO、Co2O3、Co3O4等。Co3O4在950°C分解为CoO。[4]

可溶性钴盐和氢氧化钠反应,可以得到氢氧化钴(Co(OH)2):[5]

Co(NO3)2 + 2 NaOH → Co(OH)2↓ + 2 NaNO3

氢氧化钴在碱性条件下可以被氧化至Co(III)化合物CoO(OH)。

氮族元素化合物

新制的钴粉和反应,生成Co2N和Co3N两种氮化物。钴和可以直接化合物,生成Co2P、CoP、CoAs2等物质。[2]叠氮化钴(Co(N3)2)是钴和氮的另一种二元化合物,加热时可以发生爆炸。钴(II)和叠氮根可以形成Co(N
3
)2−
4
配合物。[6]钴的五唑化物(Co(N5)2)于2017年发现,它以水合物[Co(H2O)4(N5)2]·4H2O的形式存在。它在50~145°C分解,生成叠氮化钴,脱去水并放出氮气,进一步加热发生爆炸。该化合物可由(N5)6(H3O)3(NH4)4Cl[7]或[Na(H2O)(N5)]·2H2O[8][Co(H2O)6](NO3)2于室温反应得到。水的氢键作用使该分子稳定。[8]

钴可以很容易地和硝酸反应,生成硝酸钴(Co(NO3)2)。硝酸钴存在无水物和水合物,其中水合物以六水合物最为常见,它可从溶液中析出得到。六水合硝酸钴(Co(NO3)2·6H2O)是红色潮解性晶体,易溶于水,[9]其分子中包含钴(II)的水合离子([Co(H2O)6]2+)和游离的硝酸根离子。[10]

有机化合物

维生素B12的分子结构

维生素B12是一个以钴元素为中心的有机生物分子,可溶于水,参与核酸神经递质的甲基化和合成。[11]主要来源为草食性动物的内脏或肉类。[12]

八羰基二钴(Co2(CO)8)是一种橙红色晶体,在溶液中存在两种异构体:[13]

它和氢气发生化合反应,生成HCo(CO)4或NaCo(CO)4

二茂钴(Co(C5H5)2)是环戊二烯配合物,它具有19个价电子,容易通过反应被氧化为18电子稳定结构的Co(C
5
H
5
)+
2
[14]

参考文献

  1. ^ Greenwood, Norman Neill; Earnshaw, Alan. Chemistry of the elements. 2016: 1119–1120. ISBN 978-0-7506-3365-9. OCLC 1040112384 (英语). 
  2. ^ 2.0 2.1 申泮文 等. 无机化学丛书 第九卷 锰分族 铁系 铂系. 科学出版社, 2017. ISBN 9787030305459
  3. ^ Holleman, A. F.; Wiberg, E.; Wiberg, N. (2007). "Cobalt". Lehrbuch der Anorganischen Chemie (in German) (102nd ed.). de Gruyter. pp. 1146–1152. ISBN 978-3-11-017770-1.
  4. ^ US 4389339页面存档备份,存于互联网档案馆), James, Leonard E.; Crescentini, Lamberto & Fisher, William B., "Process for making a cobalt oxide catalyst"
  5. ^ O. Glemser "Cobalt(II) Hydroxide" in Handbook of Preparative Inorganic Chemistry, 2nd Ed. Edited by G. Brauer, Academic Press, 1963, NY. Vol. 1. p. 1521.
  6. ^ Senise P. On the Reaction between Cobalt (II) and Azide Ions in Aqueous and Aqueous-organic Solutions1[J]. Journal of the American Chemical Society, 1959, 81(16): 4196-4199. DOI: 10.1021/ja01525a020
  7. ^ Chong Zhang, et al. A Symmetric Co(N5)2(H2O)4⋅4H2O High-Nitrogen Compound Formed by Cobalt(II) Cation Trapping of a Cyclo-N5 Anion. Angewandte Chemie International Edition. 2017. DOI: 10.1002/anie.201701070
  8. ^ 8.0 8.1 Yuangang Xu, et al. A series of energetic metal pentazolate hydrates. Nature. 2017. DOI: 10.1038/nature23662
  9. ^ John Dallas Donaldson, Detmar Beyersmann, "Cobalt and Cobalt Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005. doi:10.1002/14356007.a07_281.pub2
  10. ^ Prelesnik, P. V.; Gabela, F.; Ribar, B.; Krstanovic, I. (1973). "Hexaaquacobalt(II) nitrate". Cryst. Struct. Commun. 2 (4): 581–583.
  11. ^ Miller, Ariel; Korem, Maya; Almog, Ronit; Galboiz, Yanina (June 15, 2005). "Vitamin B12, demyelination, remyelination and repair in multiple sclerosis". Journal of the Neurological Sciences. 233(1-2): 93–97. PMID 15896807. doi:10.1016/j.jns.2005.03.009 – via PubMed.
  12. ^ 陈辉.现代营养学.北京:化学工业出版社,2005:76
  13. ^ Ray L. Sweany and Theodore L. Brown "Infrared spectra of matrix-isolated dicobalt octacarbonyl. Evidence for the third isomer" Inorganic Chemistry 1977, 16, pp 415 - 421. doi:10.1021/ic50168a037
  14. ^ Connelly, N. G.; Geiger, W. E. Chemical Redox Agents for Organometallic Chemistry. Chem. Rev. 1996, 96 (2): 877–910. PMID 11848774. doi:10.1021/cr940053x.

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