硫醇盐
硫醇盐是硫醇失去巯基的氢后和金属离子、金属簇或非金属离子形成的盐。
合成及反应
[编辑]碱金属的硫醇盐通常可由相应的硫醇和更强的碱（如醇盐、有机金属等）反应得到，例如：[1][2]
- iPrSH + KOtBu → iPrSK + tBuOH
- nBuSH + nBuLi → nBuSLi + C4H10
和硫亲和力较高的金属离子（如Cu+、Ag+等）则可直接由硫醇和相应的金属盐反应得到。[3]
- MSR + R'X → RSR' + MX（M为金属，X为卤素）
例如，乙硫醇钠和2-碘萘在钯配合物催化下反应，可以得到2-乙硫基萘。[4]
硫醇盐列表
[编辑]已被报道的硫醇盐参见下表：
| 化合物 | 化学式 | 外观 | 空间群 | 注释 | 参考文献 |
|---|---|---|---|---|---|
| 1,3-二甲基咪唑鎓叔丁硫醇盐 | [C5H9N2][StC4H9] | 浅黄色 | P21/n（100 K） | m.p. 110.9 °C | [5] |
| 甲硫醇锌 | Zn(SCH3)2 | 白色 | [6] | ||
| 乙硫醇锌 | Zn(SC2H5)2 | 白色 | [6] | ||
| 甲硫醇镉 | Cd(SCH3)2 | [6] | |||
| 丁硫醇汞 | Hg(SC4H9)2 | 透明四方双锥 | I41/a（207 K） | [7] | |
| 环五(乙二硫醇镍) | (NiSC2H4S)5 | 黑色针状 | C2/c | [8] | |
| 环六(二异戊硫醇镍) | Ni6S12C60H130 | 黑色块状 | P1 | [8] | |
| 环[四(乙二硫基)四(叔丁硫基)六镍] | Ni6S12C24H52 | 黑色棱柱 | [8] | ||
| 环[四(丙二硫基)四(叔丁硫基)六镍] | Ni6S12C28H60 | 黑色针状 | C2221 | [8] | |
| 四[乙氧基(N-甲基亚氨基)甲硫醇铜(I)] | [Cu2(C4H8NOS)2]2 | 黄色片状 | C2/c | [9] |
参考文献
[编辑]- ^ Chi Zhang; et al. Nickel(II) Thiolate Complexes with a Flexible cyclo-{Ni10S20} Framework. Angew Chem Int Ed, 2006. 45 (23): 3768-3772. doi:10.1002/anie.200600319.
- ^ E. C. Ashby; et al. Single electron transfer in reactions of alkyl halides with lithium thiolates. J. Org. Chem. 1985, 50, 25, 5184–5193. doi:10.1021/jo00225a041.
- ^ Bowmaker, GA; Tan, L (1979). The Preparation and Low-Frequency Vibrational Spectra of Some Copper(I) and Silver(I) Alkane- and Arene-monothiolate Complexes. Australian Journal of Chemistry, 32(7), 1443–1452. doi:10.1071/CH9791443.
- ^ Thomas Scattolin; et al. Site-Selective C−S Bond Formation at C−Br over C−OTf and C−Cl Enabled by an Air-Stable, Easily Recoverable, and Recyclable Palladium(I) Catalyst. Angew Chem Int Ed. 2018. 57 (38). 12425-12429. doi:10.1002/anie.201806036.
- ^ Jannick Guschlbauer; et al. Systematic study on anion–cation interactions via doubly ionic H-bonds in 1,3-dimethylimidazolium salts comprising chalcogenolate anions MMIm [ER] (E = S, Se; R = H, tBu, SiMe3). Dalton Trans., 2019,48, 10971-10978. doi:10.1039/C9DT01586H.
- ^ 6.0 6.1 6.2 Kohtaro Osakada; Takakazu Yamamoto. Preparation of zinc sulfide and cadmium sulfide by thermal degradation of (methanethiolato)zinc and cadmium complexes, [M(SMe)2]n (M = Zn, Cd). Inorg. Chem. 1991, 30, 10, 2328–2332. doi:10.1021/ic00010a020
- ^ C. Stålhandske and F. Zintl (1987). Structure of bis(1-butanethiolato)mercury(II). Acta Cryst, C43 (5), 863–865. doi:10.1107/s0108270187093788.
- ^ 8.0 8.1 8.2 8.3 Chunhong Tan; et al. Penta and hexanuclear nickel tiara-like clusters with two different thiolate bridges. CrystEngComm, 2015,17, 5110-5115. doi:10.1039/C5CE00863H.
- ^ T. Kuroda-Sowa; et al. Tetrakis[{μ3-ethoxy(N-methylimino)methanethiolato}copper(I)]. Acta Cryst. (1994). C50, 1026-1028. doi:10.1107/S0108270193013083.