三溴化錸

三溴化錸
別名	溴化錸(III)
識別
CAS號	13569-49-8 ; 33517-16-7（三聚體）
PubChem	83579
ChemSpider	15750935
SMILES	Br[Re](Br)Br;
InChI	1S/3BrH.Re/h3*1H;/q;;;+3/p-3;
性質
化學式	Re3Br9
摩爾質量	425.92 g·mol⁻¹
外觀	黑色有光澤的固體，其丙酮溶液為暗紅色
熔點	500 °C（升華）
溶解性（水）	反應
溶解性	微溶於乙醚和丙酮，與甲醇和氨反應
結構
分子構型	三聚體
熱力學
ΔfHm⦵298K	-164.4 kJ/mol
相關物質
其他陰離子	三氯化錸
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

三溴化錸是一種無機化合物，化學式為Re₃Br₉，它是有光澤的黑色固體，可以和水反應，生成二氧化錸。它與三氯化錸同構。^[1]^[5]

製備[編輯]

三溴化錸可由金屬錸和溴在500 °C的氮氣中反應得到：^[3]

6Re + 9Br₂ → 2Re₃Br₉

當氧存在時，會生成氧溴化錸(III)。^[3]

更常用的製備方法是利用六溴合錸(IV)酸鉀與硝酸銀的反應，生成的六溴合錸(IV)酸銀在600 °C分解，得到該化合物：^[1]^[4]

K₂ReBr₆ + 2AgNO₃ → Ag₂ReBr₆ + 2KNO₃

6Ag₂ReBr₆ → 12AgBr + 3Br₂ + 2Re₃Br₉

反應[編輯]

三溴化錸在丙酮中和三苯基膦（或三苯基胂）反應，可以得到紫色的Ph₃ERe₃Br₉（E=P, As）。^[6]吡啶可以將其還原，生成暗綠色的[Re₃Br₆(py)₃]_n。^[2]

它和疊氮化鈉在氯化銫存在下於甲醇中反應，可以得到Cs₃[Re₃Br₃(N₃)₉]·H₂O。^[7]它和氰化鈉在氯化銫存在下反應，可以得到Cs₄Na[Re₃Br₃(CN)₉]·5.25H₂O。^[8]

參考文獻[編輯]

^ ^1.0 ^1.1 ^1.2 ^1.3 ^1.4 Richard J. Thompson; Ronnie E. Foster; James L. Booker; Stephen J. Lippard. Rhenium(III) Bromide. Muetterties, Earl (編). Inorganic Syntheses. Inorganic Syntheses 10. McGraw-Hill, Inc. 1967: 58–61. ISBN 9780470132418. doi:10.1002/9780470132418.ch9 （英語）.
^ ^2.0 ^2.1 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.
^ ^3.0 ^3.1 ^3.2 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 （德語）.
^ ^4.0 ^4.1 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 （英語）.
^ 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 （英語）.
^ 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.
^ 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.
^ 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] 1.0 ^1.1 ^1.2 ^1.3 ^1.4 Richard J. Thompson; Ronnie E. Foster; James L. Booker; Stephen J. Lippard. Rhenium(III) Bromide. Muetterties, Earl (編). Inorganic Syntheses. Inorganic Syntheses 10. McGraw-Hill, Inc. 1967: 58–61. ISBN 9780470132418. doi:10.1002/9780470132418.ch9 （英語）.

[glicksman-2] 2.0 ^2.1 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] 3.0 ^3.1 ^3.2 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 （德語）.

[thermo-4] 4.0 ^4.1 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 （英語）.

[structure-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 （英語）.

[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.

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