二硫化一氢

化合物

二硫化一氢是一种短寿命的自由基,化学式为HS2,最初于1950年在光谱中检测到。[1]

二硫化一氢
英文名 thiosulfeno
识别
CAS号 14541-24-3  checkY
性质
化学式 HS2
摩尔质量 65.14 g·mol−1
相关物质
其他阴离子 超氧化氢(HO2
二硫化氢(H2S2
相关化学品 一氧化硫(SO)
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。

制备

编辑

HS2可以在纯H2S或H2S/Ar混合物的气相脉冲辐射分解中产生,而H2S/H2体系中无法观测到HS2[2]

在H2S和氟原子(氦气稀释)的反应中有HS2自由基产生。[1]氢(5-10 Pa)和氦(100-150 Pa)的混合气体经过100W的微波放电,通过150 °C下的熔硫也能得到HS2,若用同位素反应,亦有DS2生成。[3]此外,在低温下对H2S2光解的过程中可以观测到巯基自由基的产生:H2S2hv.→ 2 HS,巯基一产生便会迅速和H2S2发生反应,生成HS2:HS + H2S2 → H2S + HS2[4]

其它反应还包括S2+甲硫醇的反应:[5]

S2+ + CH3SH → CH2SH+ + HS2

结构

编辑

HS2分子中,HS键长1.3523 Å,SS键长1.9603 Å,H-S-S键角101.74°,[6]它具有2A″对称性。[7]

相关物种

编辑

烷基取代的RS2自由基(R=CH3、C2H5等)发现可以在γ-辐射的二硫化物或紫外线照射的硫醇的固体基质的热退火中产生。[8]HS2+阳离子可在S+和H2S的反应中作为副产物生成。[5]超硫化物阴离子S2可以在配合物中作为配体参与配位。[9]

三硫化一氢(HS3)及其阴离子(HS3)于2008年首次被检测到,在HS3+/0/−物种中,HS-SS键长(2.046-2.148)比相应的氧类似物HO-OO键长(1.384-1.857)要长。[10]

参考文献

编辑
  1. ^ 1.0 1.1 S.H. Ashworth, K.M. Evenson, J.M. Brown. Identification and Analysis of the Far-Infrared Laser Magnetic Resonance Spectrum of the HS2 Radical. Journal of Molecular Spectroscopy. 1995-07, 172 (1): 282–295 [2019-10-31]. doi:10.1006/jmsp.1995.1176. (原始内容存档于2018-06-02) (英语). 
  2. ^ Ole John Nielsen. Chemical kinetics in the gas-phase pulse radiolysis of hydrogen sulfide systems页面存档备份,存于互联网档案馆) (PDF). Risoe Natl. Lab., [Rep.] Risoe-M (Den.), 1979. M-2216. pp 35. ISSN: 0418-6435
  3. ^ S. H. Ashworth, E. H. Fink. The high resolution Fourier-transform chemiluminescence spectrum of the HS 2 radical. Molecular Physics. 2007-03-10, 105 (5-7): 715–725 [2019-10-31]. ISSN 0026-8976. doi:10.1080/00268970601146880 (英语). 
  4. ^ D. A. Stiles, W. J. R. Tyerman, O. P. Strausz, H. E. Gunning. PHOTOLYSIS OF GROUP VI HYDRIDES: I. SOLID H 2 S, H 2 S 2 , AND D 2 S. Canadian Journal of Chemistry. 1966-09-15, 44 (18): 2149–2155 [2019-10-31]. ISSN 0008-4042. doi:10.1139/v66-325 (英语). 
  5. ^ 5.0 5.1 Brian K. Decker, Nigel G. Adams. Selected ion flow tube studies of S2+ reactions with a series of organic molecules. International Journal of Mass Spectrometry and Ion Processes. 1997-11,. 165-166: 257–269 [2019-10-31]. doi:10.1016/S0168-1176(97)00187-0. (原始内容存档于2018-06-28) (英语). 
  6. ^ Joseph S. Francisco. Sulfur atom exchange in the reaction of SH radicals with S atoms. The Journal of Chemical Physics. 2007-06-07, 126 (21): 214301 [2019-10-31]. ISSN 0021-9606. doi:10.1063/1.2735299. (原始内容存档于2019-11-05) (英语). 
  7. ^ Zachary T. Owens, Joseph D. Larkin, Henry F. Schaefer. Hydrogen bridging in the compounds X2H (X=Al,Si,P,S). The Journal of Chemical Physics. 2006-10-28, 125 (16): 164322 [2019-10-31]. ISSN 0021-9606. doi:10.1063/1.2363375 (英语). 
  8. ^ Razskazovskii, Yu. V.; Mel'nikov, M. Ya. Mechanism of thermal formation of RS2 radicals in irradiated solutions of thiols and alkyl sulfides in solid phase. Khimicheskaya Fizika, 1989. 8 (11): 1513-1521. ISSN: 0207-401X.
  9. ^ R. C. Elder, Mitchell. Trkula. Crystal structure of decaammine[.mu.-dithio-5:5')]diruthenium tetrachloride dihydrate. A structural trans effect and evidence for a supersulfide S2- bridge. Inorganic Chemistry. 1977-05, 16 (5): 1048–1051 [2019-10-31]. ISSN 0020-1669. doi:10.1021/ic50171a017. (原始内容存档于2019-10-30) (英语). 
  10. ^ Giulia de Petris, Antonella Cartoni, Marzio Rosi, Anna Troiani. The HSSS Radical and the HSSS − Anion. The Journal of Physical Chemistry A. 2008-09-11, 112 (36): 8471–8477 [2019-10-31]. ISSN 1089-5639. doi:10.1021/jp8055637 (英语). 

拓展阅读

编辑

  1. R. P. A. Bettens, H.-H. Lee, Eric Herbst. The importance of classes of neutral-neutral reactions in the production of complex interstellar molecules. The Astrophysical Journal. 1995-04, 443: 664 [2019-10-31]. ISSN 0004-637X. doi:10.1086/175558. (原始内容存档于2018-06-12) (英语). 
  2. A.B. Sannigrahi. On the geometry of HSO, SOH and HS2 radicals in their ground and first excited electronic states. Journal of Molecular Structure. 1978-04, 44 (2): 223–229 [2019-10-31]. doi:10.1016/0022-2860(78)87032-X. (原始内容存档于2018-06-14) (英语). 
  3. Mohammad Solimannejad, Steve Scheiner. Nature of interactions in open-shell complexes pairing H 2 X with HXX, X=S,O. Molecular Physics. 2009-04-20, 107 (8-12): 713–719 [2019-10-31]. ISSN 0026-8976. doi:10.1080/00268970802397944. (原始内容存档于2022-05-08) (英语). 
  4. B. Edhay, S. Lahmar, Z. Ben Lakhdar, M. Hochlaf. Spectroscopy and metastability of the HSS − anion§. Molecular Physics. 2007-05-10, 105 (9): 1115–1122 [2019-10-31]. ISSN 0026-8976. doi:10.1080/00268970701196975 (英语). 
  5. Alan Hinchliffe. Structure and properties of HOO, HOS, HSO, HSS, FSO, FOS and FSS. Journal of Molecular Structure. 1980-09, 66: 235–242 [2019-10-31]. doi:10.1016/0022-2860(80)80178-5. (原始内容存档于2018-06-29) (英语).