一氧化硫

一氧化硫
Skeletal formula of sulfur monoxide	Spacefill model of sulfur monoxide
	IUPAC名; Sulfur monoxide[來源請求]
	系统名; Oxidosulfur
识别
CAS号	13827-32-2
PubChem	114845
ChemSpider	102805
SMILES	O=S;
InChI	1/OS/c1-2;
InChIKey	XTQHKBHJIVJGKJ-UHFFFAOYAK
Beilstein	7577656
Gmelin	666
ChEBI	45822
MeSH	sulfur+monoxide
性质
化学式	SO
摩尔质量	48.064 g·mol⁻¹
外观	无色气体
溶解性（水）	反应
log P	0.155
偶极矩	1.55 D
热力学
ΔfHm⦵298K	6.3 kJ mol-1
S⦵298K	221.94 J K-1 mol-1
危险性
NFPA 704	4 3 4
相关物质
相关化学品	三线态氧
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

一氧化硫是一种无机化合物，化学式为SO。它只能以低浓度气体存在。当浓缩或进入凝聚相，它会二聚成S₂O₂。在太空已经检测到一氧化硫，但是很少有完整分子存在。

结构和成键

一氧化硫的基态和O₂和S₂相似，为三线态。也就是说，一氧化硫中有两个不成对的电子。^[4]其中的S−O 键长是148.1 pm，和其它低氧化硫（例如S₈O中的S−O键长为148 pm）的键长类似，但比气态S₂O（146 pm）、SO₂（143.1 pm）和SO₃（142 pm）的键长长。^[4]

近红外线可以将一氧化硫激发到单线态（没有不成对电子）。它的反应性比基态三线态高，就和单线态氧比三线态氧更具反应性一样。^[5]

生产和反应

作为有机合成试剂的一氧化硫的生产主要集中在使用可以“挤出”SO的化合物。这些化合物包括相对简单的氧化硫丙环（英语：ethylene episulfoxide）^[6]或是C₁₀H₆S₃O^[7]的分解：

C₂H₄SO → C₂H₄ + SO

SO分子是热力学不稳定的，会二聚成S₂O₂。^[4]SO会和烯烃、炔烃和二烯加成，形成环硫化物，也就是有含硫三元环的化合物。^[8]

在极端条件下的产生

在实验室中，一氧化硫可以通过二氧化硫和硫蒸汽辉光放电（英语：glow discharge）而成。^[4]在含有一些溶解的惰性气体的浓硫酸单气泡声致发光中也检测到了一氧化硫。^[9]

一氧化硫基于以下反应的化学发光：^[10]

SO + O₃ → SO₂* + O₂

SO₂* → SO₂ + hν

其中*指激发态。

存在

作为配体

SO配体可以以多种方式键合：^[11]^[12]

角形M−O−S结构的终端配体，例如氟氧化钛的配体^[13]
角形M−S−O结构的终端配体，类似角形的亚硝基配体
通过硫原子和两个或三个金属中心桥接，例如Fe₃(μ³-S)(μ³-SO)(CO)₉
与钒、铌和钽的η²侧向配位（d–π相互作用）^[14]

天体化学

人们已经在木星的卫星之一木卫一周围的大气^[15]和等离子体环面^[16]中检测到一氧化硫。它也存在于金星的大气中，^[17]海尔-波普彗星中^[18]和星际物质里。^[19]

在木卫一中，一氧化硫被认为是由火山活动和光化学路径生成的。主要光化学反应如下：^[20]

O + S₂ → S + SO

SO₂ → SO + O

一氧化硫也被发现存在于天鹅座NML。^[21]

生物化学

一氧化硫可能具有一些生物活性。从反应产物羰基硫和二氧化硫推断，猪的冠状动脉中有瞬态的一氧化硫。^[22]

双阳离子

二氧化硫 SO₂在六甲苯 C₆(CH₃)₆存在下可以被超强酸 HF·AsF₅质子化，产生非刚性的π配合物（英语：Pi complex） C₆(CH₃)₆SO²⁺。其中的SO²⁺阳离子可以在苯环上无障碍移动。这个双阳离子的S−O键长为142.4(2) pm。^[23]

C₆(CH₃)₆ + SO₂ + 3 HF·AsF₅ → [C₆(CH₃)₆SO][AsF₆]₂ + [H₃O][AsF₆]

二聚体

一氧化硫会二聚成二氧化二硫（S₂O₂）。^[24]它是一种平面型分子，对称群 C_2v。它的S-S键长为202.45 pm，S−O键长为145.8 pm，比一氧化硫单体的短。它的O−S−S键角为112.7°。 S₂O₂的偶极矩为3.17 D。^[24]

参考资料

^ sulfur monoxide (CHEBI:45822). Chemical Entities of Biological Interest. UK: European Bioinformatics Institute. [2011-08-28]. （原始内容存档于2013-07-07）.
^ Lide, David R. (编). CRC Handbook of Chemistry and Physics 90th. Boca Raton, Florida: CRC Press（英语：CRC Press）. 2009: 9-52. ISBN 978-1-4200-9084-0 （英语）.
^ Lide, David R. (编). CRC Handbook of Chemistry and Physics 90th. Boca Raton, Florida: CRC Press（英语：CRC Press）. 2009: 5-16. ISBN 978-1-4200-9084-0 （英语）.
^ ^4.0 ^4.1 ^4.2 ^4.3 Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements 2nd. Oxford:Butterworth-Heinemann. 1997. ISBN 0-7506-3365-4.
^ Salama, F.; Frei, H. J. Near-Infrared-Light-Induced Reaction of Singlet SO with Allene and Dimethylacetylene in a Rare Gas Matrix. Infrared Spectra of Two Novel Episulfoxides. Journal of Physical Chemistry. 1989, 93: 1285–1292. doi:10.1021/j100341a023.
^ Chao, P.; Lemal, D. M. Sulfur Monoxide Chemistry. The Nature of SO from Thiirane Oxide and the Mechanism of Its Reaction with Dienes. Journal of the American Chemical Society. 1973, 95 (3): 920. doi:10.1021/ja00784a049.
^ Grainger, R. S.; Procopio, A.; Steed, J. W. A Novel Recyclable Sulfur Monoxide Transfer Reagent. Organic Letters. 2001, 3 (22): 3565–3568. PMID 11678709. doi:10.1021/ol016678g.
^ Nakayama, J.; Tajima, Y.; Piao, X.-H.; Sugihara, Y. [1+2] Cycloadditions of Sulfur Monoxide (SO) to Alkenes and Alkynes and [1+4]Cycloadditions to Dienes (Polyenes). Generation and Reactions of Singlet SO?. Journal of the American Chemical Society. 2007, 129 (23): 7250–7251. PMID 17506566. doi:10.1021/ja072044e.
^ Suslick, K. S.; Flannigan, D. J. The temperatures of single-bubble sonoluminescence (A). The Journal of the Acoustical Society of America. 2004, 116 (4): 2540. Bibcode:2004ASAJ..116.2540S. doi:10.1121/1.4785135.
^ Benner, R. L.; Stedman, D. H. Chemical Mechanism and Efficiency of the Sulfur Chemiluminescence Detector. Applied Spectroscopy. 1994, 48 (7): 848–851. Bibcode:1994ApSpe..48..848B. S2CID 98849015. doi:10.1366/0003702944029901.
^ Schenk, W. A. Sulfur Oxides as Ligands in Coordination Compounds. Angewandte Chemie International Edition in English 26: 98–109. 1987. doi:10.1002/anie.198700981.
^ Woollins, J. D. Sulfur: Inorganic Chemistry. Encyclopedia of Inorganic Chemistry. John Wiley and Sons. 1995. ISBN 0-471-93620-0.
^ Wei, R.; Chen, X.; Gong, Y. End-On Oxygen-Bound Sulfur Monoxide Complex of Titanium Oxyfluoride. Inorganic Chemistry. 2019, 58 (17): 11801–11806. PMID 31441297. doi:10.1021/acs.inorgchem.9b01880.
^ Wei, R.; Chen, X.; Gong, Y. Side-On Sulfur Monoxide Complexes of Tantalum, Niobium, and Vanadium Oxyfluorides. Inorganic Chemistry. 2019, 58 (6): 3807–3814. PMID 30707575. doi:10.1021/acs.inorgchem.8b03411.
^ Lellouch, E. Io's atmosphere: Not yet understood. Icarus. 1996, 124: 1–21. doi:10.1006/icar.1996.0186.
^ Russell, C. T.; Kivelson, M. G. Detection of SO in Io's Exosphere. Science. 2000, 287 (5460): 1998–1999. Bibcode:2000Sci...287.1998R. PMID 10720321. doi:10.1126/science.287.5460.1998.
^ Na, C. Y.; Esposito, L. W.; Skinner, T. E. International Ultraviolet Explorer observations of Venus SO₂ and SO. Journal of Geophysical Research. 1990, 95: 7485–7491. Bibcode:1990JGR....95.7485N. doi:10.1029/JD095iD06p07485.
^ Lis, D. C.; Mehringer, D. M.; Benford, D.; Gardner, M.; Phillips, T. G.; Bockelée-Morvan, D.; Biver, N.; Colom, P.; Crovisier, J.; Despois, D.; Rauer, H. New Molecular Species in Comet C/1995 O1 (Hale–Bopp) Observed with the Caltech S submillimeter Observatory. Earth, Moon, and Planets. 1997, 78 (1–3): 13–20. Bibcode:1997EM&P...78...13L. S2CID 51862359. doi:10.1023/A:1006281802554.
^ Gottlieb, C. A.; Gottlieb, E. W.; Litvak, M. M.; Ball, J. A.; Pennfield, H. Observations of interstellar sulfur monoxide. Astrophysical Journal. 1978, 1 (219): 77–94. Bibcode:1978ApJ...219...77G. doi:10.1086/155757.
^ Moses, J. I.; Zolotov, M. Y.; Fegley, B. Photochemistry of a Volcanically Driven Atmosphere on Io: Sulfur and Oxygen Species from a Pele-Type Eruption. Icarus. 2002, 156 (1): 76–106. Bibcode:2002Icar..156...76M. doi:10.1006/icar.2001.6758.
^ Marvel, Kevin. NML Cygni. The Circumstellar Environment of Evolved Stars As Revealed by Studies of Circumstellar Water Masers. Universal Publishers. 1996: 182–212 [23 August 2012]. ISBN 978-1-58112-061-5. （原始内容存档于2022-03-08）.
^ Balazy, M.; Abu-Yousef, I. A.; Harpp, D. N.; Park, J. Identification of carbonyl sulfide and sulfur dioxide in porcine coronary artery by gas chromatography/mass spectrometry, possible relevance to EDHF. Biochemical and Biophysical Research Communications. 2003, 311 (3): 728–734. PMID 14623333. doi:10.1016/j.bbrc.2003.10.055.
^ Malischewski, Moritz; Seppelt, Konrad. Isolation and Characterization of a Non-Rigid Hexamethylbenzene-SO²⁺ Complex (PDF). Angewandte Chemie International Edition. 2017, 56 (52): 16495–16497 [2021-12-26]. ISSN 1433-7851. PMID 29084371. doi:10.1002/anie.201708552. （原始内容 (PDF)存档于2021-12-26）（英语）.
^ ^24.0 ^24.1 Lovas, F. J.; Tiemann, E.; Johnson, D. R. Spectroscopic studies of the SO₂ discharge system. II. Microwave spectrum of the SO dimer. The Journal of Chemical Physics. 1974, 60 (12): 5005–5010. Bibcode:1974JChPh..60.5005L. doi:10.1063/1.1681015.

[1] sulfur monoxide (CHEBI:45822). Chemical Entities of Biological Interest. UK: European Bioinformatics Institute. [2011-08-28]. （原始内容存档于2013-07-07）.

[2] Lide, David R. (编). CRC Handbook of Chemistry and Physics 90th. Boca Raton, Florida: CRC Press（英语：CRC Press）. 2009: 9-52. ISBN 978-1-4200-9084-0 （英语）.

[3] Lide, David R. (编). CRC Handbook of Chemistry and Physics 90th. Boca Raton, Florida: CRC Press（英语：CRC Press）. 2009: 5-16. ISBN 978-1-4200-9084-0 （英语）.

[greenwood-4] 4.0 ^4.1 ^4.2 ^4.3 Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements 2nd. Oxford:Butterworth-Heinemann. 1997. ISBN 0-7506-3365-4.

[5] Salama, F.; Frei, H. J. Near-Infrared-Light-Induced Reaction of Singlet SO with Allene and Dimethylacetylene in a Rare Gas Matrix. Infrared Spectra of Two Novel Episulfoxides. Journal of Physical Chemistry. 1989, 93: 1285–1292. doi:10.1021/j100341a023.

[6] Chao, P.; Lemal, D. M. Sulfur Monoxide Chemistry. The Nature of SO from Thiirane Oxide and the Mechanism of Its Reaction with Dienes. Journal of the American Chemical Society. 1973, 95 (3): 920. doi:10.1021/ja00784a049.

[7] Grainger, R. S.; Procopio, A.; Steed, J. W. A Novel Recyclable Sulfur Monoxide Transfer Reagent. Organic Letters. 2001, 3 (22): 3565–3568. PMID 11678709. doi:10.1021/ol016678g.

[8] Nakayama, J.; Tajima, Y.; Piao, X.-H.; Sugihara, Y. [1+2] Cycloadditions of Sulfur Monoxide (SO) to Alkenes and Alkynes and [1+4]Cycloadditions to Dienes (Polyenes). Generation and Reactions of Singlet SO?. Journal of the American Chemical Society. 2007, 129 (23): 7250–7251. PMID 17506566. doi:10.1021/ja072044e.

[9] Suslick, K. S.; Flannigan, D. J. The temperatures of single-bubble sonoluminescence (A). The Journal of the Acoustical Society of America. 2004, 116 (4): 2540. Bibcode:2004ASAJ..116.2540S. doi:10.1121/1.4785135.

[10] Benner, R. L.; Stedman, D. H. Chemical Mechanism and Efficiency of the Sulfur Chemiluminescence Detector. Applied Spectroscopy. 1994, 48 (7): 848–851. Bibcode:1994ApSpe..48..848B. S2CID 98849015. doi:10.1366/0003702944029901.

[11] Schenk, W. A. Sulfur Oxides as Ligands in Coordination Compounds. Angewandte Chemie International Edition in English 26: 98–109. 1987. doi:10.1002/anie.198700981.

[12] Woollins, J. D. Sulfur: Inorganic Chemistry. Encyclopedia of Inorganic Chemistry. John Wiley and Sons. 1995. ISBN 0-471-93620-0.

[13] Wei, R.; Chen, X.; Gong, Y. End-On Oxygen-Bound Sulfur Monoxide Complex of Titanium Oxyfluoride. Inorganic Chemistry. 2019, 58 (17): 11801–11806. PMID 31441297. doi:10.1021/acs.inorgchem.9b01880.

[14] Wei, R.; Chen, X.; Gong, Y. Side-On Sulfur Monoxide Complexes of Tantalum, Niobium, and Vanadium Oxyfluorides. Inorganic Chemistry. 2019, 58 (6): 3807–3814. PMID 30707575. doi:10.1021/acs.inorgchem.8b03411.

[15] Lellouch, E. Io's atmosphere: Not yet understood. Icarus. 1996, 124: 1–21. doi:10.1006/icar.1996.0186.

[16] Russell, C. T.; Kivelson, M. G. Detection of SO in Io's Exosphere. Science. 2000, 287 (5460): 1998–1999. Bibcode:2000Sci...287.1998R. PMID 10720321. doi:10.1126/science.287.5460.1998.

[17] Na, C. Y.; Esposito, L. W.; Skinner, T. E. International Ultraviolet Explorer observations of Venus SO₂ and SO. Journal of Geophysical Research. 1990, 95: 7485–7491. Bibcode:1990JGR....95.7485N. doi:10.1029/JD095iD06p07485.

[18] Lis, D. C.; Mehringer, D. M.; Benford, D.; Gardner, M.; Phillips, T. G.; Bockelée-Morvan, D.; Biver, N.; Colom, P.; Crovisier, J.; Despois, D.; Rauer, H. New Molecular Species in Comet C/1995 O1 (Hale–Bopp) Observed with the Caltech S submillimeter Observatory. Earth, Moon, and Planets. 1997, 78 (1–3): 13–20. Bibcode:1997EM&P...78...13L. S2CID 51862359. doi:10.1023/A:1006281802554.

[19] Gottlieb, C. A.; Gottlieb, E. W.; Litvak, M. M.; Ball, J. A.; Pennfield, H. Observations of interstellar sulfur monoxide. Astrophysical Journal. 1978, 1 (219): 77–94. Bibcode:1978ApJ...219...77G. doi:10.1086/155757.

[20] Moses, J. I.; Zolotov, M. Y.; Fegley, B. Photochemistry of a Volcanically Driven Atmosphere on Io: Sulfur and Oxygen Species from a Pele-Type Eruption. Icarus. 2002, 156 (1): 76–106. Bibcode:2002Icar..156...76M. doi:10.1006/icar.2001.6758.

[Marvel1996-21] Marvel, Kevin. NML Cygni. The Circumstellar Environment of Evolved Stars As Revealed by Studies of Circumstellar Water Masers. Universal Publishers. 1996: 182–212 [23 August 2012]. ISBN 978-1-58112-061-5. （原始内容存档于2022-03-08）.

[22] Balazy, M.; Abu-Yousef, I. A.; Harpp, D. N.; Park, J. Identification of carbonyl sulfide and sulfur dioxide in porcine coronary artery by gas chromatography/mass spectrometry, possible relevance to EDHF. Biochemical and Biophysical Research Communications. 2003, 311 (3): 728–734. PMID 14623333. doi:10.1016/j.bbrc.2003.10.055.

[23] Malischewski, Moritz; Seppelt, Konrad. Isolation and Characterization of a Non-Rigid Hexamethylbenzene-SO²⁺ Complex (PDF). Angewandte Chemie International Edition. 2017, 56 (52): 16495–16497 [2021-12-26]. ISSN 1433-7851. PMID 29084371. doi:10.1002/anie.201708552. （原始内容 (PDF)存档于2021-12-26）（英语）.

[lovas-24] 24.0 ^24.1 Lovas, F. J.; Tiemann, E.; Johnson, D. R. Spectroscopic studies of the SO₂ discharge system. II. Microwave spectrum of the SO dimer. The Journal of Chemical Physics. 1974, 60 (12): 5005–5010. Bibcode:1974JChPh..60.5005L. doi:10.1063/1.1681015.

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