三溴化铼

三溴化铼
别名	溴化铼(III)
识别
CAS号	13569-49-8 ; 33517-16-7（三聚体）
PubChem	83579
ChemSpider	15750935
SMILES	Br[Re](Br)Br;
InChI	1S/3BrH.Re/h3*1H;/q;;;+3/p-3;
性质
化学式	Re3Br9
摩尔质量	425.92 g·mol⁻¹
外观	黑色有光泽的固体，其丙酮溶液为暗红色
熔点	500 °C（升华）
溶解性（水）	反应
溶解性	微溶于乙醚和丙酮，与甲醇和氨反应
结构
分子构型	三聚体
热力学
ΔfHm⦵298K	-164.4 kJ/mol
相关物质
其他阴离子	三氯化铼
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

三溴化铼是一种无机化合物，化学式为Re₃Br₉，它是有光泽的黑色固体，可以和水反应，生成二氧化铼。它与三氯化铼同构。^[1]^[5]

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制备

三溴化铼可由金属铼和溴在500 °C的氮气中反应得到：^[3]

6Re + 9Br₂ → 2Re₃Br₉

当氧存在时，会生成氧溴化铼(III)。^[3]

更常用的制备方法是利用六溴合铼(IV)酸钾与硝酸银的反应，生成的六溴合铼(IV)酸银在600 °C分解，得到该化合物：^[1]^[4]

K₂ReBr₆ + 2AgNO₃ → Ag₂ReBr₆ + 2KNO₃

6Ag₂ReBr₆ → 12AgBr + 3Br₂ + 2Re₃Br₉

反应

三溴化铼在丙酮中和三苯基膦（或三苯基胂）反应，可以得到紫色的Ph₃ERe₃Br₉（E=P, As）。^[6]吡啶可以将其还原，生成暗绿色的[Re₃Br₆(py)₃]_n。^[2]

它和叠氮化钠在氯化铯存在下于甲醇中反应，可以得到Cs₃[Re₃Br₃(N₃)₉]·H₂O。^[7]它和氰化钠在氯化铯存在下反应，可以得到Cs₄Na[Re₃Br₃(CN)₉]·5.25H₂O。^[8]

参考文献

[1]
Richard J. Thompson; Ronnie E. Foster; James L. Booker; Stephen J. Lippard. Rhenium(III) Bromide. Muetterties, Earl (编). Inorganic Syntheses. Inorganic Syntheses 10. McGraw-Hill, Inc. 1967: 58–61. ISBN 9780470132418. doi:10.1002/9780470132418.ch9 （英语）.
[2]
Glicksman, H.D.; Walton, R.A. The redox behavior of rhenium halides. X. The reduction of rhenium(III) bromide by tertiary amines and phosphines. Inorganica Chimica Acta. January 1976, 19: 91–94. ISSN 0020-1693. doi:10.1016/S0020-1693(00)91079-X.
[3]
Harro Hagen; Adolf Sieverts. Rheniumtribromid. Zeitschrift für anorganische und allgemeine Chemie (Verlag GmbH & Co. KGaA, Weinheim). 1933, 215 (1): 111–112. doi:10.1002/zaac.19332150114 （德语）.
[4]
J. P. King; J. W. Cobble. The Thermodynamic Properties of Technetium and Rhenium Compounds. VII. Heats of Formation of Rhenium Trichloride and Rhenium Tribromide. Free Energies and Entropies. Journal of the American Chemical Society. 1960, 82 (9): 2111–2113. doi:10.1021/ja01494a005 （英语）.
[5]
V. V. Ugarov. Electron-diffraction investigation of the structure of the Re₃Br₉ molecule. Journal of Structural Chemistry. 1971, 12 (2): 286–288. S2CID 100857081. doi:10.1007/BF00739116 （英语）.
[6]
Cotton, F. A.; Lippard, S. J.; Mague, J. T. Preparation and Spectra of Some Adducts of the Nonachlorotrirhenium and Nonabromotrirhenium Groups; Evidence for the Re₃Br₉ Group. Inorganic Chemistry. April 1965, 4 (4): 508–514. ISSN 0020-1669. doi:10.1021/ic50026a015. eISSN 1520-510X.
[7]
Yarovoy, Spartak S.; Mirzaeva, Irina V.; Mironov, Yuri V.; Pervukhina, Natalia V.; Brylev, Konstantin A. The Cluster Polyazide Complexes: Synthesis, Crystal Structures, and ¹⁴N NMR Studies of [{Re₃(μ-X)₃}(N₃)₉]^3– (X = Br or I). Inorganic Chemistry. 27 July 2022, 61 (31): 12442–12448. ISSN 0020-1669. PMID 35894216. doi:10.1021/acs.inorgchem.2c01949. eISSN 1520-510X.
[8]
Yarovoy, Spartak S.; Gayfulin, Yakov M.; Smolentsev, Anton I.; Yanshole, Vadim V.; Mironov, Yuri V. Stabilization of Re₃⁷⁺/Re₃⁸⁺ Metalloclusters by Cyanide Ligands in New Trinuclear Rhenium Cluster Complexes [{Re₃X₃}(CN)₉]^4–/[{Re₃X₃}(CN)₉]^5– (X = Br or I). Inorganic Chemistry. 6 April 2021, 60 (8): 5980–5987. ISSN 0020-1669. PMID 33821642. doi:10.1021/acs.inorgchem.1c00399. eISSN 1520-510X.

[rebr3-1] [1]
Richard J. Thompson; Ronnie E. Foster; James L. Booker; Stephen J. Lippard. Rhenium(III) Bromide. Muetterties, Earl (编). Inorganic Syntheses. Inorganic Syntheses 10. McGraw-Hill, Inc. 1967: 58–61. ISBN 9780470132418. doi:10.1002/9780470132418.ch9 （英语）.

[glicksman-2] [2]
Glicksman, H.D.; Walton, R.A. The redox behavior of rhenium halides. X. The reduction of rhenium(III) bromide by tertiary amines and phosphines. Inorganica Chimica Acta. January 1976, 19: 91–94. ISSN 0020-1693. doi:10.1016/S0020-1693(00)91079-X.

[german-3] [3]
Harro Hagen; Adolf Sieverts. Rheniumtribromid. Zeitschrift für anorganische und allgemeine Chemie (Verlag GmbH & Co. KGaA, Weinheim). 1933, 215 (1): 111–112. doi:10.1002/zaac.19332150114 （德语）.

[thermo-4] [4]
J. P. King; J. W. Cobble. The Thermodynamic Properties of Technetium and Rhenium Compounds. VII. Heats of Formation of Rhenium Trichloride and Rhenium Tribromide. Free Energies and Entropies. Journal of the American Chemical Society. 1960, 82 (9): 2111–2113. doi:10.1021/ja01494a005 （英语）.

[structure-5] [5]
V. V. Ugarov. Electron-diffraction investigation of the structure of the Re₃Br₉ molecule. Journal of Structural Chemistry. 1971, 12 (2): 286–288. S2CID 100857081. doi:10.1007/BF00739116 （英语）.

[6] [6]
Cotton, F. A.; Lippard, S. J.; Mague, J. T. Preparation and Spectra of Some Adducts of the Nonachlorotrirhenium and Nonabromotrirhenium Groups; Evidence for the Re₃Br₉ Group. Inorganic Chemistry. April 1965, 4 (4): 508–514. ISSN 0020-1669. doi:10.1021/ic50026a015. eISSN 1520-510X.

[7] [7]
Yarovoy, Spartak S.; Mirzaeva, Irina V.; Mironov, Yuri V.; Pervukhina, Natalia V.; Brylev, Konstantin A. The Cluster Polyazide Complexes: Synthesis, Crystal Structures, and ¹⁴N NMR Studies of [{Re₃(μ-X)₃}(N₃)₉]^3– (X = Br or I). Inorganic Chemistry. 27 July 2022, 61 (31): 12442–12448. ISSN 0020-1669. PMID 35894216. doi:10.1021/acs.inorgchem.2c01949. eISSN 1520-510X.

[8] [8]
Yarovoy, Spartak S.; Gayfulin, Yakov M.; Smolentsev, Anton I.; Yanshole, Vadim V.; Mironov, Yuri V. Stabilization of Re₃⁷⁺/Re₃⁸⁺ Metalloclusters by Cyanide Ligands in New Trinuclear Rhenium Cluster Complexes [{Re₃X₃}(CN)₉]^4–/[{Re₃X₃}(CN)₉]^5– (X = Br or I). Inorganic Chemistry. 6 April 2021, 60 (8): 5980–5987. ISSN 0020-1669. PMID 33821642. doi:10.1021/acs.inorgchem.1c00399. eISSN 1520-510X.

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