環辛二烯氯化銥二聚體

環辛二烯氯化銥二聚體
別名	Bis(1,5-cyclooctadiene)diiridium(I) dichloride
識別
CAS號	12112-67-3
PubChem	5365616（化學式錯誤）
ChemSpider	21171240
SMILES	C1/C=C\CC/C=C\C1.C1/C=C\CC/C=C\C1.[Cl].[Cl].[Ir].[Ir];
性質
化學式	C16H24Cl2Ir2
摩爾質量	671.70 g·mol⁻¹
外觀	紅橙色固體
密度	2.65 g/cm3（紅色同質異形體）
危險性
	GHS危險性符號;
GHS提示詞	Warning
H-術語	H302, H312, H315, H319, H335
P-術語	P261, P264, P270, P271, P280, P301+312, P302+352, P304+340, P305+351+338, P312, P321, P322, P330, P332+313
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

環辛二烯氯化銥二聚體是一種有機銥化合物（英語：organoiridium compound），分子式為[Ir(μ²-Cl)(COD)]₂，其中COD是1,5-環辛二烯（C₈H₁₂）。它是紅橙色固體，可溶於有機溶劑。該絡合物是其他銥絡合物的前體，其中有一些可用於均相催化。^[1]該固體在空氣中穩定，但其溶液在空氣中會降解。

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製備、結構和反應

將溶於醇溶劑中的水合三氯化銥和環辛二烯加熱，可製得這個化合物。過程中，Ir(III)被還原成Ir(I)。^[2]

就分子結構而言，與其他d⁸複合物一樣，銥中心是正方形平面。Ir₂Cl₂中心呈摺疊形狀，二面角為86°。該分子以黃橙色和紅橙色同質異形體結晶，其中第二個較為常見。^[3]^[4]

環辛二烯氯化銥二聚體廣泛用作其他銥絡合物的前體，其中Crabtree催化劑較為人熟知。^[5]氯配體也可以替換成甲醇鹽，得到環辛二烯甲醇銥二聚體（Ir₂(OCH₃)₂(C₈H₁₂)₂）。^[6]環辛二烯配體在(C₈H₈)IrL₂]⁺之類的陽離子絡合物中容易異構化。^[7]

參見

雙(環辛烯)氯化銥二聚體（英語：Chlorobis(cyclooctene)iridium dimer）
氯化環辛二烯基銠二聚物

參考文獻

[1]
J. Hartwig, "Organotransition Metal Chemistry: From Bonding to Catalysis" University Science Books, 2009. ISBN 978-1891389535.
[2]
Herdé, J. L.; Lambert, J. C.; Senoff, C. V. Cyclooctene and 1,5-Cyclooctadiene Complexes of Iridium(I). Inorganic Syntheses 15. 1974: 18–20. ISBN 9780470132463. doi:10.1002/9780470132463.ch5.
[3]
F. Albert Cotton, Pascual Lahuerta, Mercedes Sanau, Willi Schwotzer "Air oxidation of Ir₂(Cl)₂(COD)₂ revisited. The structures of [Ir(μ²-Cl)(COD)]₂ (ruby form) and its oxidation product, Ir₂Cl₂(COD)₂(μ₂-OH)₂(μ²-O)" Inorganica Chimica Acta, 1986 vol. 120, Pages 153–157. doi:10.1016/S0020-1693(00)86102-2
[4]
Tabrizi, D., Manoli, J. M., Dereigne, A., "Etude radiocristallographique de μ-dichloro-bis (π cyclooctadiène-1,5) diiridium: [(COD-1,5)IrCl]₂, variété jaune-orange", Journal of the Less Common Metals 1970, vol. 21, pp. 337. doi:10.1016/0022-5088(70)90155-4
[5]
Crabtree, Robert H.; Morehouse, Sheila M. [η4 -1,5-Cyclooctadiene)(Pyridine)-(Tricyclohexylphosphine)Iridium(I)Hexafluorophosphate. Inorganic Syntheses 24. 1986: 173–176. ISBN 9780470132555. doi:10.1002/9780470132555.ch50.
[6]
Uson, R.; Oro, L. A.; Cabeza, J. A. Dinuclear Methoxy, Cyclooctadiene, and Barrelene Complexes of Rhodium(I) and Iridium(I). Inorganic Syntheses 23. 1985: 126–130. ISBN 9780470132548. doi:10.1002/9780470132548.ch25.
[7]
Martín, Marta; Sola, Eduardo; Torres, Olga; Plou, Pablo; Oro, Luis A. Versatility of Cyclooctadiene Ligands in Iridium Chemistry and Catalysis. Organometallics. 2003, 22 (26): 5406–5417. doi:10.1021/om034218g.

[1] [1]
J. Hartwig, "Organotransition Metal Chemistry: From Bonding to Catalysis" University Science Books, 2009. ISBN 978-1891389535.

[2] [2]
Herdé, J. L.; Lambert, J. C.; Senoff, C. V. Cyclooctene and 1,5-Cyclooctadiene Complexes of Iridium(I). Inorganic Syntheses 15. 1974: 18–20. ISBN 9780470132463. doi:10.1002/9780470132463.ch5.

[3] [3]
F. Albert Cotton, Pascual Lahuerta, Mercedes Sanau, Willi Schwotzer "Air oxidation of Ir₂(Cl)₂(COD)₂ revisited. The structures of [Ir(μ²-Cl)(COD)]₂ (ruby form) and its oxidation product, Ir₂Cl₂(COD)₂(μ₂-OH)₂(μ²-O)" Inorganica Chimica Acta, 1986 vol. 120, Pages 153–157. doi:10.1016/S0020-1693(00)86102-2

[4] [4]
Tabrizi, D., Manoli, J. M., Dereigne, A., "Etude radiocristallographique de μ-dichloro-bis (π cyclooctadiène-1,5) diiridium: [(COD-1,5)IrCl]₂, variété jaune-orange", Journal of the Less Common Metals 1970, vol. 21, pp. 337. doi:10.1016/0022-5088(70)90155-4

[5] [5]
Crabtree, Robert H.; Morehouse, Sheila M. [η4 -1,5-Cyclooctadiene)(Pyridine)-(Tricyclohexylphosphine)Iridium(I)Hexafluorophosphate. Inorganic Syntheses 24. 1986: 173–176. ISBN 9780470132555. doi:10.1002/9780470132555.ch50.

[6] [6]
Uson, R.; Oro, L. A.; Cabeza, J. A. Dinuclear Methoxy, Cyclooctadiene, and Barrelene Complexes of Rhodium(I) and Iridium(I). Inorganic Syntheses 23. 1985: 126–130. ISBN 9780470132548. doi:10.1002/9780470132548.ch25.

[7] [7]
Martín, Marta; Sola, Eduardo; Torres, Olga; Plou, Pablo; Oro, Luis A. Versatility of Cyclooctadiene Ligands in Iridium Chemistry and Catalysis. Organometallics. 2003, 22 (26): 5406–5417. doi:10.1021/om034218g.

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