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拟卤素

拟卤素类卤素pseudohalogen)是一类性质类似卤素无机化合物,其通式为 XY,其中 X 可以是氰基 CN氰氧基 OCN硫氰基 SCN 等官能基,而 Y 可以是上述的物质或是卤素原子。如氰气 (CN)2碘化氰 ICN 等都是拟卤素。拟卤素的特性是其官能基的反应类似卤素,而且官能基中的双键三键不影响其化学特性。

纳米团簇的(也被称为超原子)有时也被视为拟卤素,因为其化学性质和卤素离子类似,而且会形成 Al13I2(类似 I3)及其他的化合物。这是由于小尺度下金属键的作用所造成。

另一种类卤素的配合物八羰基二钴 Co2(CO)8,(理论上)可视为四羰基钴 Co(CO)4双体。它可以分解为四羰基钴离子 Co(CO)4-。HCo(CO)4 其实是相当强的,不过因为其对水的溶解度低,以至它的酸性比氢卤酸要弱。

金负离子由于和碱作用发生歧化反应,以及能与氢原子形成共价键,被认为是一种拟卤素离子。[1]

性质

拟卤素的一些性质列入下表:

拟卤素的性质
基团 游离态 离子 对应的酸 相关反应
Cl (参照) Cl2 Cl HCl(强酸) Ag+ + ClAgCl↓(白色)
2 Na + Cl2 → 2 NaCl
CN (CN)2 CN- HCN(弱酸) Ag+ + CN-AgCN↓(白色)
CP (CP)2 CP- HCP
OCN 氧氰 OCN- 氰酸根 HOCN Ag+ + OCNAgOCN
SCN 硫氰 (SCN)2 HSCN Ag+ + SCNAgSCN↓(白色)
OSCN英语Hypothiocyanite HOSCN(弱酸)
SeCN 硒氰 (SeCN)2 SeCN
TeCN 碲氰 不存在 TeCN-
OH 羟基 H2O2 OH H2O
SH 巯基 H2S2 SH- H2S
NO2 硝基
二氧化氮自由基
N2O4 NO2- HNO2
N3 叠氮 N3- HN3 Ag+ + N3AgN3
Co(CO)4 Co2(CO)8 HCo(CO)4 2 Na + Co2(CO)8 → 2 NaCo(CO)4
C(CN)3 C2(CN)6 C(CN)3- HC(CN)3
CS2N3[2] (CS2N3)2 CS2N3- HCS2N3

拟卤素和卤素类似,有氧化性,也有形成配合物的能力。卤素和拟卤素、拟卤素和拟卤素之间也可以形成“互卤化物”,如BrCN等。

参考资料

  1. ^ Mudring, Anjy-Verena; Jansen, Martin. ChemInform Abstract: Base-Induced Disproportionation of Elemental Gold.. ChemInform. 2000-11-28, 31 (48): no–no. doi:10.1002/chin.200048020. 
  2. ^ Margaret-Jane Crawford, et al. CS2N3, A Novel Pseudohalogen. J. Am. Chem. Soc. 2000, 122, 9052-9053
  • New Scientist, issue 2495 (16th April 2005), pp30–33, "A new kind of alchemy", Philip Ball.
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拟卤素
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