十羰基二錸

十羰基二錸
	IUPAC名; bis(pentacarbonylrhenium)(Re—Re)
別名	羰基錸、五羰基錸
識別
CAS號	14285-68-8
PubChem	518917
ChemSpider	436546
SMILES	[Re].[Re].[C-]#[O+].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-];
InChI	1/10CO.2Re/c10*1-2;;;
InChIKey	ZIZHEHXAMPQGEK-UHFFFAOYAX
性質
化學式	Re2(CO)10
摩爾質量	652.52 g/mol g·mol⁻¹
熔點	170 °C（443 K）
溶解性（水）
危險性
警示術語	R：R20
安全術語	S：S36
歐盟分類	有害（Xn）
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

十羰基二錸是一種無機化合物，分子式為Re₂(CO)₁₀。它可以購得，經常用作合成各種錸羰基配合物的起點。它首次於1941年由瓦爾特·希貝爾記錄，他通過將錸還原羰基化製備這個化合物。^[1]十羰基二錸中有一對由一個Re-Re鍵連接的四角錐形Re(CO)₅單元，形成一個全同羰基配合物。^[2]

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結構及性質

十羰基二錸的晶體結構相當熟知。化合物由一對四角錐形的Re(CO)₅單位組成，而它們由一個Re-Re鍵連接。此處可以發生兩種構象：交錯式和重疊式。重疊式構象佔所有構象的30%，它會產生一個D_4h點群，但點群為D_4d的交錯式比較穩定。Re-Re鍵長通過實驗發現為3.04Å。^[3]

合成

十羰基二錸可以由七氧化二錸（Re₂O₇）在350 atm和250 °C下還原羰基化製備。

Re₂O₇ + 17 CO → Re₂(CO)₁₀ + 7 CO₂

反應

羰基配體可以被其他如膦和亞磷酸鹽的配體（以L標記）置換。^[4]

Re₂(CO)₁₀ + 2 L → Re₂(CO)₈L₂

這個化合物也可以通過鹵化「破裂」成單核Re(I)羰基配合物：^[5]

Re₂(CO)₁₀ + X₂ → 2 Re(CO)₅X (X = Cl, Br, I)

加入溴就會生成五羰基溴化錸。它是許多錸配合物的中間體。這個化合物也可以氫化生成各種多錸配合物，最終得到錸元素。^[6]

Re₂(CO)₁₀ → H₃Re₃(CO)₁₂ → H₅Re₄(CO)₁₂ → Re (metal)

十羰基二錸遇水時，就會經過光解作用轉化為羥基配合物：^[7]

Re₂(CO)₁₀ → HRe(CO)₅ + Re₄(CO)₁₂(OH)₄

應用

錸基催化作用可用於複分解反應、重整、氫化以及各種如加氫脫硫的加氫處理過程。^[8]十羰基二錸可以用來促進醇的矽烷化（silylation）並製備矽醚，其反應為：^[9]

RSiH₃ + R'OH → RH₂SiOR' + H₂

參見

金屬羰基配合物

參考文獻

[1]
W. Hieber; H. Fuchs. Über Metallcarbonyle. XXXVIII. Über Rheniumpentacarbonyl. Zeitschrift für anorganische und allgemeine Chemie. 1941, 248 (3): 256–268. doi:10.1002/zaac.19412480304 （德語）.
[2]
F. Armstrong; J. Rourke; M. Hagerman; M. Weller; P. Atkins; T. Overton. Shiver and Atkins' Inorganic Chemistry 5th edition: 555. 2010.
[3]
M. Churchill; K. Amoh; H. Wasserman. Redetermination of the crystal structure of dimanganese decacarbonyl and determination of the crystal structure of dirhenium decacarbonyl. Revised values for the manganese-manganese and rhenium-rhenium bond lengths in dimanganese decacarbonyl and dirhenium decacarbonyl. Inorganic Chemistry. 1981, 20 (3): 1609–1612. doi:10.1021/ic50219a056.
[4]
K.S. Suslick; P.F. Schubert. Sonochemistry of dimanganese decacarbonyl (Mn₂(CO)₁₀) and dirhenium decacarbonyl (Re₂(CO)₁₀). Journal of the American Chemical Society. 1983, 105 (19): 6042–6044. doi:10.1021/ja00357a014.
[5]
Steven P. Schmidt; William C. Trogler; Fred Basolo. Pentacarbonylrhenium Halides. Inorganic Syntheses 28. 2007: 154–159. ISBN 9780470132593. doi:10.1002/9780470132593.ch42.
[6]
C. Dossi, J. Schaefer, W. M. H. Sachtler. Mechanism of particle formation in decomposing Re₂(CO)₁₀ on NaY and NaHY zeolites: effect of prereduced Pt clusters in the supercages. Journal of Molecular Catalysis. 1989, 52 (1): 193–209. doi:10.1016/0304-5102(89)80089-6.
[7]
D. R. Gard; T. L. Brown. Photochemical reactions of dirhenium decacarbonyl with water. Journal of the American Chemical Society. 1982, 104 (23): 6340–6347. doi:10.1021/ja00387a031.
[8]
R. Jarkko; A.P. Tapani. Controlled gas-phase preparation and HDS activity of Re₂(CO)₁₀ alumina catalysts. Catalysis Letters. 2000, 65 (4): 175–180. S2CID 96952765. doi:10.1023/A:1019006413873.
[9]
D.H.R.Barton, M.J. Kelly. Mechanism and utility of the dirhenium decacarbonyl catalyzed formation of silyl ethers. Tetrahedron Letters. 1992, 33 (35): 5041–5044. doi:10.1002/chin.199302225.

[german-1] [1]
W. Hieber; H. Fuchs. Über Metallcarbonyle. XXXVIII. Über Rheniumpentacarbonyl. Zeitschrift für anorganische und allgemeine Chemie. 1941, 248 (3): 256–268. doi:10.1002/zaac.19412480304 （德語）.

[2] [2]
F. Armstrong; J. Rourke; M. Hagerman; M. Weller; P. Atkins; T. Overton. Shiver and Atkins' Inorganic Chemistry 5th edition: 555. 2010.

[3] [3]
M. Churchill; K. Amoh; H. Wasserman. Redetermination of the crystal structure of dimanganese decacarbonyl and determination of the crystal structure of dirhenium decacarbonyl. Revised values for the manganese-manganese and rhenium-rhenium bond lengths in dimanganese decacarbonyl and dirhenium decacarbonyl. Inorganic Chemistry. 1981, 20 (3): 1609–1612. doi:10.1021/ic50219a056.

[4] [4]
K.S. Suslick; P.F. Schubert. Sonochemistry of dimanganese decacarbonyl (Mn₂(CO)₁₀) and dirhenium decacarbonyl (Re₂(CO)₁₀). Journal of the American Chemical Society. 1983, 105 (19): 6042–6044. doi:10.1021/ja00357a014.

[5] [5]
Steven P. Schmidt; William C. Trogler; Fred Basolo. Pentacarbonylrhenium Halides. Inorganic Syntheses 28. 2007: 154–159. ISBN 9780470132593. doi:10.1002/9780470132593.ch42.

[6] [6]
C. Dossi, J. Schaefer, W. M. H. Sachtler. Mechanism of particle formation in decomposing Re₂(CO)₁₀ on NaY and NaHY zeolites: effect of prereduced Pt clusters in the supercages. Journal of Molecular Catalysis. 1989, 52 (1): 193–209. doi:10.1016/0304-5102(89)80089-6.

[7] [7]
D. R. Gard; T. L. Brown. Photochemical reactions of dirhenium decacarbonyl with water. Journal of the American Chemical Society. 1982, 104 (23): 6340–6347. doi:10.1021/ja00387a031.

[8] [8]
R. Jarkko; A.P. Tapani. Controlled gas-phase preparation and HDS activity of Re₂(CO)₁₀ alumina catalysts. Catalysis Letters. 2000, 65 (4): 175–180. S2CID 96952765. doi:10.1023/A:1019006413873.

[9] [9]
D.H.R.Barton, M.J. Kelly. Mechanism and utility of the dirhenium decacarbonyl catalyzed formation of silyl ethers. Tetrahedron Letters. 1992, 33 (35): 5041–5044. doi:10.1002/chin.199302225.

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