一氧化硫
一氧化硫 | |||
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IUPAC名 Sulfur monoxide[來源請求] | |||
系統名 Oxidosulfur[1] | |||
識別 | |||
CAS號 | 13827-32-2 ![]() | ||
PubChem | 114845 | ||
ChemSpider | 102805 | ||
SMILES |
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InChI |
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InChIKey | XTQHKBHJIVJGKJ-UHFFFAOYAK | ||
Beilstein | 7577656 | ||
Gmelin | 666 | ||
ChEBI | 45822 | ||
MeSH | sulfur+monoxide | ||
性質 | |||
化學式 | SO | ||
莫耳質量 | 48.064 g·mol⁻¹ | ||
外觀 | 無色氣體 | ||
溶解性(水) | 反應 | ||
log P | 0.155 | ||
偶極矩 | 1.55 D[2] | ||
熱力學 | |||
ΔfHm⦵298K | 6.3 kJ mol-1[3] | ||
S⦵298K | 221.94 J K-1 mol-1 | ||
危險性 | |||
NFPA 704 | |||
相關物質 | |||
相關化學品 | 三線態氧 | ||
若非註明,所有數據均出自標準狀態(25 ℃,100 kPa)下。 |
一氧化硫是一種無機化合物,化學式為SO。它只能以低濃度氣體存在。當濃縮或進入凝聚相,它會二聚成S2O2。在太空已經檢測到一氧化硫,但是很少有完整分子存在。
結構和成鍵
[編輯]一氧化硫的基態和O2和S2相似,為三線態。也就是說,一氧化硫中有兩個不成對的電子。[4]其中的S−O 鍵長是148.1 pm,和其它低氧化硫(例如S8O中的S−O鍵長為148 pm)的鍵長類似,但比氣態S2O(146 pm)、SO2(143.1 pm)和SO3(142 pm)的鍵長長。[4]
近紅外線可以將一氧化硫激發到單線態(沒有不成對電子)。它的反應性比基態三線態高,就和單線態氧比三線態氧更具反應性一樣。[5]
生產和反應
[編輯]作為有機合成試劑的一氧化硫的生產主要集中在使用可以「擠出」SO的化合物。這些化合物包括相對簡單的氧化硫丙環[6]或是C10H6S3O[7]的分解:
- C2H4SO → C2H4 + SO
SO分子是熱力學不穩定的,會二聚成S2O2。[4]SO會和烯烴、炔烴和二烯加成,形成環硫化物,也就是有含硫三元環的化合物。[8]
在極端條件下的產生
[編輯]在實驗室中,一氧化硫可以通過二氧化硫和硫蒸汽輝光放電而成。[4]在含有一些溶解的惰性氣體的濃硫酸單氣泡聲致發光中也檢測到了一氧化硫。[9]
- SO + O3 → SO2* + O2
- SO2* → SO2 + hν
其中*指激發態。
存在
[編輯]作為配體
[編輯]- 角形M−O−S結構的終端配體,例如氟氧化鈦的配體[13]
- 角形M−S−O結構的終端配體,類似角形的亞硝基配體
- 通過硫原子和兩個或三個金屬中心橋接,例如Fe3(μ3-S)(μ3-SO)(CO)9
- 與釩、鈮和鉭的η2側向配位(d–π相互作用)[14]
天體化學
[編輯]人們已經在木星的衛星之一木衛一周圍的大氣[15]和電漿體環面[16]中檢測到一氧化硫。它也存在於金星的大氣中,[17]海爾-波普彗星中[18]和星際物質里。[19]
在木衛一中,一氧化硫被認為是由火山活動和光化學路徑生成的。主要光化學反應如下:[20]
- O + S2 → S + SO
- SO2 → SO + O
生物化學
[編輯]一氧化硫可能具有一些生物活性。從反應產物羰基硫和二氧化硫推斷,豬的冠狀動脈中有瞬態的一氧化硫。[22]
雙陽離子
[編輯]二氧化硫 SO2在六甲苯 C6(CH3)6存在下可以被超強酸HF·AsF5質子化,產生非剛性的π配合物 C6(CH3)6SO2+。其中的SO2+陽離子可以在苯環上無障礙移動。這個雙陽離子的S−O鍵長為142.4(2) pm。[23]
- C6(CH3)6 + SO2 + 3 HF·AsF5 → [C6(CH3)6SO][AsF6]2 + [H3O][AsF6]
二聚體
[編輯]![](http://upload.wikimedia.org/wikipedia/commons/thumb/d/d6/Disulfur-dioxide-2D-dimensions.png/150px-Disulfur-dioxide-2D-dimensions.png)
![](http://upload.wikimedia.org/wikipedia/commons/thumb/3/34/Disulfur-dioxide-3D-vdW-A.png/150px-Disulfur-dioxide-3D-vdW-A.png)
一氧化硫會二聚成二氧化二硫(S2O2)。[24]它是一種平面型分子,對稱群 C2v。它的S-S鍵長為202.45 pm,S−O鍵長為145.8 pm,比一氧化硫單體的短。它的O−S−S鍵角為112.7°。 S2O2的偶極矩為3.17 D。[24]
參考資料
[編輯]- ^ sulfur monoxide (CHEBI:45822). Chemical Entities of Biological Interest. UK: European Bioinformatics Institute. [2011-08-28]. (原始內容存檔於2013-07-07).
- ^ Lide, David R. (編). CRC Handbook of Chemistry and Physics 90th. Boca Raton, Florida: CRC Press. 2009: 9-52. ISBN 978-1-4200-9084-0 (英語).
- ^ Lide, David R. (編). CRC Handbook of Chemistry and Physics 90th. Boca Raton, Florida: CRC Press. 2009: 5-16. ISBN 978-1-4200-9084-0 (英語).
- ^ 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. (原始內容存檔於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. (原始內容 (PDF)存檔於2021-12-26) (英語).
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