硫代磷酰溴

硫代磷酰溴
别名	三溴硫化磷
识别
CAS号	3931-89-3
PubChem	77530
ChemSpider	69937
SMILES	S=P(Br)(Br)Br;
性质
化学式	PSBr; 3
摩尔质量	302.75 g·mol⁻¹
外观	黄色晶体
密度	2.97 g cm−3
熔点	37.8 °C（311 K）
沸点	212 °C（485 K）（分解）
结构
晶体结构	立方晶系
空间群	Pa3, No. 205
晶格常数	a = 11.03 Å
相关物质
相关化学品	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（英语：Phosphorothioic chloride difluoride）;
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

硫代磷酰溴是化学式PSBr
3的无机化合物。^[1]

制备

硫代磷酰溴可以由三溴化磷和十硫化四磷或是硫单质在惰性气氛中一起加热到130 °C而成。^[3]

它也是P
4S
7和溴在低溫的二硫化碳中反应的产物之一。^[1]

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

结构和性质

硫代磷酰溴是四面体形分子，分子对称性C_3v。气相电子衍射（英语：gas electron diffraction）表明硫代磷酰溴的P-S键长为1.895 Å、P-Br键长为2.193 Å、S=P–Br键角为116.2°、Br–P–Br键角则为101.9°。^[4]

硫代磷酰溴可溶于二硫化碳、氯仿和乙醚。^[3]

反应

硫代磷酰溴容易水解，发生亲核取代反应以及和路易斯酸形成加合物。^[5]它和碘化锂的反应会产生PSBr
2I和PSBrI
2，但不会产生完全碘化的产物硫代磷酰碘 PSI
3。^[6]硫代磷酰溴在有机合成中可以把亚砜还原硫醚、^[7]把S-氧化硫酮（英语：sulfine）还原成硫酮。^[8]

参考资料

^ ^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 （英语）.
^ ICSD Entry: 39130. Cambridge Structural Database: Access Structures (Cambridge Crystallographic Data Centre). [2022-10-30]. （原始内容存档于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 （英语）.

[CSD-2] ICSD Entry: 39130. Cambridge Structural Database: Access Structures (Cambridge Crystallographic Data Centre). [2022-10-30]. （原始内容存档于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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