二氧化二硫

二氧化二硫
英文名	Disulfur dioxide
别名	一氧化硫二聚体
识别
CAS号	126885-21-0（）
PubChem	145835224
SMILES	O=[S][S]=O;
InChI	1/O2S2/c1-3-4-2;
InChIKey	AXYLJRYHRATPSG-UHFFFAOYNA-N
性质
化学式	S2O2
摩尔质量	96.1299 g·mol⁻¹
外观	气体
结构
配位几何	角形
危险性
主要危害	有毒
相关物质
相关化学品	四硫; SO; S3O; S2O
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

二氧化二硫，又称一氧化硫二聚体，是一种硫氧化物，化学式 S₂O₂。^[2]这个固体不稳定，在室温下只能存在几秒钟。^[3]

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二氧化二硫是顺式平面型结构，分子对称性为 C_2v。它的S−O键长为145.8 pm，比一氧化硫短。它的S−S键长为202.45 pm，O−S−S键角为112.7°。S₂O₂的偶极矩为3.17 D。^[4]

一氧化硫会自发可逆地二聚成二氧化二硫。^[4]因此，制备一氧化硫的方法都可以制备二氧化二硫。二氧化二硫也由二氧化硫放电而成。^[5]另一种实验室的制备方法是使氧原子与羰基硫或二硫化碳蒸气反应。^[6]

尽管硫单质的大部分形式（S₈、其它硫环和硫链）都不会和SO₂反应，原子硫会与其反应，形成一氧化硫和二聚体二氧化二硫：^[7]

S + SO₂ → S₂O₂ ⇌ 2 SO

在氦稀释的二氧化硫中，通过微波放电也会产生二氧化二硫。^[8]在0.1 mmHg（13 Pa）的压力下，S₂O₂的产率为5%。^[9]

当硫化氢和氧气发生闪光光解（英语：Flash photolysis）时，会瞬时形成二氧化二硫。^[10]

二氧化二硫的电离能是6982159096125159100♠9.93±0.02 eV。^[6]

如在金星大气层中观察到的，二氧化二硫会吸收320–400 nm处的光，^[11]并且据信促成了金星的温室效应。^[12]

尽管二氧化二硫和一氧化硫存在平衡，它会和一氧化硫反应，形成二氧化硫和一氧化二硫。^[8]^[13]

S₂O₂可作为过渡金属的配体。它的配位方式为η²-S–S，两个硫原子都和金属原子键合。^[14]这是在2003年发现的。铂的双(三甲基膦)氧化环硫乙烷（英语：thiirane S-oxide）配合物在110 °C的甲苯中加热时，会放出乙烯，形成有S₂O₂配体的(Ph₃P)₂Pt(S₂O₂)。^[15]铱也可以形成二氧化二硫配合物，它的制备方法是用高碘酸钠氧化cis-[(dppe)₂IrS₂]Cl成[(dppe)₂IrS₂O]，然后再氧化成二氧化二硫配合物[(dppe)₂IrS₂O₂]，其中dppe是1,2-双(二苯基膦)乙烷。^[16]^[17]这种物质的S₂O₂是顺式结构的。同样条件下也可以写成反式配合物，不过这个配合物含有两个分开的SO自由基。这个铱配合物会和三苯基膦反应，形成三苯基氧化膦和三苯基硫化膦。^[16]

S
2O−
2 阴离子已在气相中被观察到。它的结构应该是和SO₃类似的平面三角形分子构型。^[18]

有一些证据表明，二氧化二硫可能少量存在于金星大气层中，并且它可能对其严重的温室效应产生重大影响。^[11]在地球大气层中没有发现任何实质性数量的二氧化二硫。

[1]
Demaison, Jean; Vogt, Jürgen. 836. O₂S₂ Disulfur dioxide (PDF). Asymmetric Top Molecules, Part 3. Landolt–Börnstein: Group II Molecules and Radicals 29D3. Springer. 2011: 492. ISBN 9783642141454. doi:10.1007/978-3-642-14145-4_258.^{[失效链接]}
[2]
Holleman, Arnold F.; Wiber, Egon; Wiberg, Nils (编). Oxides of sulfur. Inorganic Chemistry. Academic Press. 2001: 530 [2021-12-26]. ISBN 9780123526519. （原始内容存档于2021-12-26）.
[3]
Mitchell, Stephen C. Biological Interactions Of Sulfur Compounds. CRC Press. 2004: 7. ISBN 9780203362525.
[4]
Lovas, F. J. Spectroscopic studies of the SO₂ discharge system. II. Microwave spectrum of the SO dimer. The Journal of Chemical Physics. 1974, 60 (12): 5005. doi:10.1063/1.1681015.
[5]
Thorwirth, Sven; Theulé, P.; Gottlieb, C. A.; Müller, H. S. P.; McCarthy, M. C.; Thaddeus, P. Rotational spectroscopy of S₂O: vibrational satellites, ³³S isotopomers, and the submillimeter-wave spectrum (PDF). Journal of Molecular Structure. 2006, 795 (1–3): 219–229 [2021-12-26]. Bibcode:2006JMoSt.795..219T. doi:10.1016/j.molstruc.2006.02.055. （原始内容 (PDF)存档于2017-08-09）. （页面存档备份，存于互联网档案馆）
[6]
Cheng, Bing-Ming; Hung, Wen-Ching. Photoionization efficiency spectrum and ionization energy of S₂O₂. The Journal of Chemical Physics. 1999, 110 (1): 188. Bibcode:1999JChPh.110..188C. ISSN 0021-9606. doi:10.1063/1.478094.
[7]
Murakami, Yoshinori; Onishi, Shouichi; Kobayashi, Takaomi; Fujii, Nobuyuki; Isshiki, Nobuyasu; Tsuchiya, Kentaro; Tezaki, Atsumu; Matsui, Hiroyuki. High Temperature Reaction of S + SO₂ → SO + SO: Implication of S₂O₂ Intermediate Complex Formation. The Journal of Physical Chemistry A. 2003, 107 (50): 10996–11000. Bibcode:2003JPCA..10710996M. ISSN 1089-5639. doi:10.1021/jp030471i.
[8]
Field, T. A.; Slattery, A. E.; Adams, D. J.; Morrison, D. D. Experimental observation of dissociative electron attachment to S₂O and S₂O₂ with a new spectrometer for unstable molecules (PDF). Journal of Physics B: Atomic, Molecular and Optical Physics. 2005, 38 (3): 255–264 [2013-05-13]. Bibcode:2005JPhB...38..255F. ISSN 0953-4075. doi:10.1088/0953-4075/38/3/009. （原始内容 (PDF)存档于2015-09-24）. （页面存档备份，存于互联网档案馆）
[9]
Sahoo, Balaram; Nayak, Nimai Charan; Samantaray, Asutosh; Pujapanda, Prafulla Kumar. Inorganic Chemistry. PHI Learning. 2012: 461 [2013-05-16]. ISBN 9788120343085. （原始内容存档于2021-12-26）. （页面存档备份，存于互联网档案馆）
[10]
Compton, R. G.; Bamford, C. H.; Tipper, C. F. H. Oxidation of H₂S. Reactions of Non-Metallic Inorganic Compounds. Comprehensive Chemical Kinetics. Elsevier. 1972: 50 [2021-12-26]. ISBN 9780080868011. （原始内容存档于2021-12-26）.
[11]
Frandsen, B. N.; Wennberg, P. O.; Kjærgaard, H. G. Identification of OSSO as a near-UV absorber in the Venusian atmosphere (PDF). Geophysical Research Letters. 2016, 43 (21): 11146–11155 [2021-12-26]. Bibcode:2016GeoRL..4311146F. doi:10.1002/2016GL070916 . （原始内容 (PDF)存档于2018-07-19）. （页面存档备份，存于互联网档案馆）
[12]
Rare molecule on Venus may help explain planet's weather. CBC News. [2016-11-11]. （原始内容存档于2018-10-18）. （页面存档备份，存于互联网档案馆）
[13]
Herron, J. T.; Huie, R. E. Rate constants at 298 K for the reactions SO + SO + M → (SO)₂ + M and SO + (SO)₂ → SO₂ + S₂O. Chemical Physics Letters. 1980, 76 (2): 322–324. Bibcode:1980CPL....76..322H. doi:10.1016/0009-2614(80)87032-1.
[14]
Halcrow, Malcolm A.; Huffman, John C.; Christou, George. Synthesis, Characterization, and Molecular Structure of the New S₂O Complex Mo(S₂O)(S₂CNEt₂)₃·1/2Et₂O (PDF). Inorganic Chemistry. 1994, 33 (17): 3639–3644 [2021-12-26]. ISSN 0020-1669. doi:10.1021/ic00095a005. （原始内容 (PDF)存档于2015-11-06）. （页面存档备份，存于互联网档案馆）
[15]
Lorenz, Ingo-Peter; Kull, Jürgen. Complex Stabilization of Disulfur Dioxide in the Fragmentation of Thiirane S-Oxide on Bis(triphenylphosphane)platinum(0). Angewandte Chemie International Edition in English. 1986, 25 (3): 261–262. ISSN 0570-0833. doi:10.1002/anie.198602611.
[16]
Schmid, Günter; Ritter, Günter; Debaerdemaeker, Tony. Die Komplexchemie niederer Schwefeloxide. II. Schwefelmonoxid und Dischwefeldioxid als Komplexliganden [The complex chemistry of lower sulfur oxides. II. Sulfur monoxide and disulfur dioxide as complex ligands]. Chemische Berichte. 1975, 108 (9): 3008–3013. ISSN 0009-2940. doi:10.1002/cber.19751080921.
[17]
Nagata, K.; Takeda, N.; Tokitoh, N. Unusual Oxidation of Dichalcogenido Complexes of Platinum. Chemistry Letters. 2003, 32 (2): 170–171. ISSN 0366-7022. doi:10.1246/cl.2003.170.
[18]
Clements, Todd G.; Hans-Jürgen Deyerl; Robert E. Continetti. Dissociative Photodetachment Dynamics of S
2O−
2 (PDF). The Journal of Physical Chemistry A. 2002, 106 (2): 279–284 [2013-05-13]. Bibcode:2002JPCA..106..279C. ISSN 1089-5639. doi:10.1021/jp013329v. （原始内容 (PDF)存档于2012-07-14）. Archive-It的存档，存档日期2012-07-14

[atm3-1] [1]
Demaison, Jean; Vogt, Jürgen. 836. O₂S₂ Disulfur dioxide (PDF). Asymmetric Top Molecules, Part 3. Landolt–Börnstein: Group II Molecules and Radicals 29D3. Springer. 2011: 492. ISBN 9783642141454. doi:10.1007/978-3-642-14145-4_258.^{[失效链接]}

[2] [2]
Holleman, Arnold F.; Wiber, Egon; Wiberg, Nils (编). Oxides of sulfur. Inorganic Chemistry. Academic Press. 2001: 530 [2021-12-26]. ISBN 9780123526519. （原始内容存档于2021-12-26）.

[3] [3]
Mitchell, Stephen C. Biological Interactions Of Sulfur Compounds. CRC Press. 2004: 7. ISBN 9780203362525.

[lovas-4] [4]
Lovas, F. J. Spectroscopic studies of the SO₂ discharge system. II. Microwave spectrum of the SO dimer. The Journal of Chemical Physics. 1974, 60 (12): 5005. doi:10.1063/1.1681015.

[Thorwirth-5] [5]
Thorwirth, Sven; Theulé, P.; Gottlieb, C. A.; Müller, H. S. P.; McCarthy, M. C.; Thaddeus, P. Rotational spectroscopy of S₂O: vibrational satellites, ³³S isotopomers, and the submillimeter-wave spectrum (PDF). Journal of Molecular Structure. 2006, 795 (1–3): 219–229 [2021-12-26]. Bibcode:2006JMoSt.795..219T. doi:10.1016/j.molstruc.2006.02.055. （原始内容 (PDF)存档于2017-08-09）. （页面存档备份，存于互联网档案馆）

[Cheng1999-6] [6]
Cheng, Bing-Ming; Hung, Wen-Ching. Photoionization efficiency spectrum and ionization energy of S₂O₂. The Journal of Chemical Physics. 1999, 110 (1): 188. Bibcode:1999JChPh.110..188C. ISSN 0021-9606. doi:10.1063/1.478094.

[Murakami2003-7] [7]
Murakami, Yoshinori; Onishi, Shouichi; Kobayashi, Takaomi; Fujii, Nobuyuki; Isshiki, Nobuyasu; Tsuchiya, Kentaro; Tezaki, Atsumu; Matsui, Hiroyuki. High Temperature Reaction of S + SO₂ → SO + SO: Implication of S₂O₂ Intermediate Complex Formation. The Journal of Physical Chemistry A. 2003, 107 (50): 10996–11000. Bibcode:2003JPCA..10710996M. ISSN 1089-5639. doi:10.1021/jp030471i.

[Field2005-8] [8]
Field, T. A.; Slattery, A. E.; Adams, D. J.; Morrison, D. D. Experimental observation of dissociative electron attachment to S₂O and S₂O₂ with a new spectrometer for unstable molecules (PDF). Journal of Physics B: Atomic, Molecular and Optical Physics. 2005, 38 (3): 255–264 [2013-05-13]. Bibcode:2005JPhB...38..255F. ISSN 0953-4075. doi:10.1088/0953-4075/38/3/009. （原始内容 (PDF)存档于2015-09-24）. （页面存档备份，存于互联网档案馆）

[PujapandaBalaram-9] [9]
Sahoo, Balaram; Nayak, Nimai Charan; Samantaray, Asutosh; Pujapanda, Prafulla Kumar. Inorganic Chemistry. PHI Learning. 2012: 461 [2013-05-16]. ISBN 9788120343085. （原始内容存档于2021-12-26）. （页面存档备份，存于互联网档案馆）

[10] [10]
Compton, R. G.; Bamford, C. H.; Tipper, C. F. H. Oxidation of H₂S. Reactions of Non-Metallic Inorganic Compounds. Comprehensive Chemical Kinetics. Elsevier. 1972: 50 [2021-12-26]. ISBN 9780080868011. （原始内容存档于2021-12-26）.

[Frandsen2016-11] [11]
Frandsen, B. N.; Wennberg, P. O.; Kjærgaard, H. G. Identification of OSSO as a near-UV absorber in the Venusian atmosphere (PDF). Geophysical Research Letters. 2016, 43 (21): 11146–11155 [2021-12-26]. Bibcode:2016GeoRL..4311146F. doi:10.1002/2016GL070916 . （原始内容 (PDF)存档于2018-07-19）. （页面存档备份，存于互联网档案馆）

[MyUser_Cbc.ca_November_11_2016c-12] [12]
Rare molecule on Venus may help explain planet's weather. CBC News. [2016-11-11]. （原始内容存档于2018-10-18）. （页面存档备份，存于互联网档案馆）

[Herron-13] [13]
Herron, J. T.; Huie, R. E. Rate constants at 298 K for the reactions SO + SO + M → (SO)₂ + M and SO + (SO)₂ → SO₂ + S₂O. Chemical Physics Letters. 1980, 76 (2): 322–324. Bibcode:1980CPL....76..322H. doi:10.1016/0009-2614(80)87032-1.

[Halcrow1994-14] [14]
Halcrow, Malcolm A.; Huffman, John C.; Christou, George. Synthesis, Characterization, and Molecular Structure of the New S₂O Complex Mo(S₂O)(S₂CNEt₂)₃·1/2Et₂O (PDF). Inorganic Chemistry. 1994, 33 (17): 3639–3644 [2021-12-26]. ISSN 0020-1669. doi:10.1021/ic00095a005. （原始内容 (PDF)存档于2015-11-06）. （页面存档备份，存于互联网档案馆）

[Lorenz1986-15] [15]
Lorenz, Ingo-Peter; Kull, Jürgen. Complex Stabilization of Disulfur Dioxide in the Fragmentation of Thiirane S-Oxide on Bis(triphenylphosphane)platinum(0). Angewandte Chemie International Edition in English. 1986, 25 (3): 261–262. ISSN 0570-0833. doi:10.1002/anie.198602611.

[Schmid1975-16] [16]
Schmid, Günter; Ritter, Günter; Debaerdemaeker, Tony. Die Komplexchemie niederer Schwefeloxide. II. Schwefelmonoxid und Dischwefeldioxid als Komplexliganden [The complex chemistry of lower sulfur oxides. II. Sulfur monoxide and disulfur dioxide as complex ligands]. Chemische Berichte. 1975, 108 (9): 3008–3013. ISSN 0009-2940. doi:10.1002/cber.19751080921.

[Nagata-17] [17]
Nagata, K.; Takeda, N.; Tokitoh, N. Unusual Oxidation of Dichalcogenido Complexes of Platinum. Chemistry Letters. 2003, 32 (2): 170–171. ISSN 0366-7022. doi:10.1246/cl.2003.170.

[Clements2002-18] [18]
Clements, Todd G.; Hans-Jürgen Deyerl; Robert E. Continetti. Dissociative Photodetachment Dynamics of S
2O−
2 (PDF). The Journal of Physical Chemistry A. 2002, 106 (2): 279–284 [2013-05-13]. Bibcode:2002JPCA..106..279C. ISSN 1089-5639. doi:10.1021/jp013329v. （原始内容 (PDF)存档于2012-07-14）. Archive-It的存档，存档日期2012-07-14

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二氧化二硫

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结构

形成

性质

反应

配合物

相关阴离子

太阳系中的二氧化二硫

参考资料