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
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：Chi Zhang; et al. Nickel(II) Thiolate Complexes with a Flexible cyclo-{Ni10S20} Framework. Angew Chem Int Ed, 2006. 45 (23): 3768-3772. .E. C. Ashby; et al. Single electron transfer in reactions of alkyl halides with lithium thiolates. J. Org. Chem. 1985, 50, 25, 5184–5193. .
 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。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. .

硫醇盐可以和卤代烃反应，得到硫醚：
 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。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. .

硫醇盐列表
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  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. .  甲硫醇锌  Zn(SCH3)2  白色      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.  乙硫醇锌  Zn(SC2H5)2  白色       甲硫醇镉  Cd(SCH3)2         丁硫醇汞  Hg(SC4H9)2  透明四方双锥   I41/a（207 K）   C. Stålhandske and F. Zintl (1987). Structure of bis(1-butanethiolato)mercury(II). Acta Cryst, C43 (5), 863–865. . 环五(乙二硫醇镍)  (NiSC2H4S)5  黑色针状   C2/c  Chunhong Tan; et al. Penta and hexanuclear nickel tiara-like clusters with two different thiolate bridges. CrystEngComm, 2015,17, 5110-5115. . 环六(二异戊硫醇镍)  Ni6S12C60H130  黑色块状  P   环[四(乙二硫基)四(叔丁硫基)六镍]  Ni6S12C24H52 黑色棱柱    环[四(丙二硫基)四(叔丁硫基)六镍]  Ni6S12C28H60 黑色针状  C2221   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 T. Kuroda-Sowa; et al. Tetrakis[{μ3-ethoxy(N-methylimino)methanethiolato}copper(I)]. Acta Cryst. (1994). C50, 1026-1028. .

参考文献

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