硫代磷酰溴

硫代磷酰溴
別名	三溴硫化磷
識別
CAS編號	3931-89-3
PubChem	77530
ChemSpider	69937
SMILES	S=P(Br)(Br)Br;
性質
化學式	PSBr; 3
摩爾質量	302.75 g·mol⁻¹
外觀	黃色晶體
密度	2.97 g cm−3
熔點	37.8 °C（311 K）
沸點	212 °C（485 K）（分解）
結構
晶體結構	立方晶系
空間群	Pa3, No. 205
晶格常數	a = 11.03 Å
相關物質
相關化學品	三溴化磷; 磷酰溴; 硫代磷酰氟; 硫代磷酰氯; 硫代磷酰碘; 二氟氯硫化磷（英語：Phosphorothioic chloride difluoride）;
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

硫代磷酰溴是化學式PSBr
3的無機化合物。^[1]

製備

硫代磷酰溴可以由三溴化磷和十硫化四磷或是硫單質在惰性氣氛中一起加熱到130 °C而成。^[3]

它也是P
4S
7和溴在低溫的二硫化碳中反應的產物之一。^[1]

1.5 P
4S
7 + 6 Br
2 → PBr
3 + PSBr
3 + P
2S
6Br
2 + P
2S
5Br
4

結構和性質

硫代磷酰溴是四面體形分子，分子對稱性C_3v。氣相電子繞射（英語：gas electron diffraction）表明硫代磷酰溴的P-S鍵長為1.895 Å、P-Br鍵長為2.193 Å、S=P–Br鍵角為116.2°、Br–P–Br鍵角則為101.9°。^[4]

硫代磷酰溴可溶於二硫化碳、氯仿和乙醚。^[3]

反應

硫代磷酰溴容易水解，發生親核取代反應以及和路易斯酸形成加合物。^[5]它和碘化鋰的反應會產生PSBr
2I和PSBrI
2，但不會產生完全碘化的產物硫代磷酰碘 PSI
3。^[6]硫代磷酰溴在有機合成中可以把亞碸還原硫醚、^[7]把S-氧化硫酮（英語：sulfine）還原成硫酮。^[8]

參考資料

^ ^1.0 ^1.1 ^1.2 Greenwood, Norman Neill; Earnshaw, Alan. Chemistry of the elements. 2016: 501–503. ISBN 978-0-7506-3365-9. OCLC 1040112384 （英語）.
^ ICSD Entry: 39130. Cambridge Structural Database: Access Structures (Cambridge Crystallographic Data Centre). [2022-10-30]. （原始內容存檔於2022-10-30）.
^ ^3.0 ^3.1 Arthur D. F. Toy. The Chemistry of Phosphorus. Permanon Texts in Inorganic Chemistry 3. Permanon Press. 1975: 438. ISBN 9781483139593.
^ Jacob, E. Jean; Danielson, Donald D.; Samdal, Svein. An electron diffraction determination of the molecular structures of phosphoryl bromide and thiophosphoryl bromide. J. Mol. Struct. 1980, 62 (2): 143–155. Bibcode:1980JMoSt..62..143J. doi:10.1016/0022-2860(80)85232-X.
^ van der Veer, W.; Jellinek, F. Adducts of thiophosphoryl compounds with metal halides. Part III: Addition compounds of phosphoryl bromide and thiophosphoryl bromide. Recl. Trav. Chim. Pays-Bas. 1970, 89 (8): 833–844. doi:10.1002/recl.19700890809.
^ Dillon, K. B.; Craveirinha Dillon, M. G.; Waddington, T. C. The identification of some new thiophosphoryl compounds containing P–I bonds by means of ³¹P N.M.R. spectroscopy. Inorg. Nucl. Chem. Lett. 1977, 13 (8): 349–353. doi:10.1016/0020-1650(77)80109-8.
^ Still, I. W. J.; Reed, J. N.; Turnbull, K. Thiophosphoryl bromide: a new reagent for the reduction of sulfoxides to sulfides. Tetrahedron Lett. 1979, 20 (17): 1481–1484. doi:10.1016/S0040-4039(01)86183-9.
^ Kuipers, J. A. M.; Lammerink, B. H. M.; Still, I . W. J.; Zwanenburg, B. Phosphorus Pentasulfide and Thiophosphoryl Bromide: Facile Reagents for the Reduction of Sulfines to Thiones. Synthesis. 1981, 1981 (4): 295–297. doi:10.1055/s-1981-29423.

[G&E-1] 1.0 ^1.1 ^1.2 Greenwood, Norman Neill; Earnshaw, Alan. Chemistry of the elements. 2016: 501–503. ISBN 978-0-7506-3365-9. OCLC 1040112384 （英語）.

[CSD-2] ICSD Entry: 39130. Cambridge Structural Database: Access Structures (Cambridge Crystallographic Data Centre). [2022-10-30]. （原始內容存檔於2022-10-30）.

[Toy-3] 3.0 ^3.1 Arthur D. F. Toy. The Chemistry of Phosphorus. Permanon Texts in Inorganic Chemistry 3. Permanon Press. 1975: 438. ISBN 9781483139593.

[4] Jacob, E. Jean; Danielson, Donald D.; Samdal, Svein. An electron diffraction determination of the molecular structures of phosphoryl bromide and thiophosphoryl bromide. J. Mol. Struct. 1980, 62 (2): 143–155. Bibcode:1980JMoSt..62..143J. doi:10.1016/0022-2860(80)85232-X.

[5] van der Veer, W.; Jellinek, F. Adducts of thiophosphoryl compounds with metal halides. Part III: Addition compounds of phosphoryl bromide and thiophosphoryl bromide. Recl. Trav. Chim. Pays-Bas. 1970, 89 (8): 833–844. doi:10.1002/recl.19700890809.

[6] Dillon, K. B.; Craveirinha Dillon, M. G.; Waddington, T. C. The identification of some new thiophosphoryl compounds containing P–I bonds by means of ³¹P N.M.R. spectroscopy. Inorg. Nucl. Chem. Lett. 1977, 13 (8): 349–353. doi:10.1016/0020-1650(77)80109-8.

[7] Still, I. W. J.; Reed, J. N.; Turnbull, K. Thiophosphoryl bromide: a new reagent for the reduction of sulfoxides to sulfides. Tetrahedron Lett. 1979, 20 (17): 1481–1484. doi:10.1016/S0040-4039(01)86183-9.

[8] Kuipers, J. A. M.; Lammerink, B. H. M.; Still, I . W. J.; Zwanenburg, B. Phosphorus Pentasulfide and Thiophosphoryl Bromide: Facile Reagents for the Reduction of Sulfines to Thiones. Synthesis. 1981, 1981 (4): 295–297. doi:10.1055/s-1981-29423.

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