乙酰丙酮釕

乙酰丙酮釕
	IUPAC名; Tris(acetylacetonato)Ruthenium (III)
別名	Ru(acac)3; 乙酰丙酮釕(III)
識別
CAS號	14284-93-6
PubChem	16057901
SMILES	CC(=O)CC(=O)C.CC(=O)CC(=O)C.CC(=O)CC(=O)C.[Ru];
InChI	1S/3C5H8O2.Ru/c31-4(6)3-5(2)7;/h33H2,1-2H3;;
性質
化學式	(C5H7O2)3Ru
摩爾質量	398.39 g·mol⁻¹
外觀	深紫色固體
密度	1.54 g/cm3
熔點	260 °C（533 K）
溶解性（水）	不溶
溶解性	可溶於大部分有機溶劑
危險性
警示術語	R：R36, R37, R38
安全術語	S：S26, S36
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

乙酰丙酮釕是一種乙酰丙酮配合物，化學式Ru(O₂C₅H₇)₃。它是一種深紫色固體，可溶於大多數有機溶劑。^[2]它可用來製備其它釕化合物。

製備[編輯]

1914年，乙酰丙酮釕通過三氯化釕和乙酰丙酮在碳酸氫鉀下的反應首次合成。^[3]從那時起，人們已經研究了替代合成路線，但原始的製備方法仍然有用：^[4]

RuCl₃•3H₂O + MeCOCH₂COMe → Ru(acac)₃ + 3 HCl + 3 H₂O

結構和性質[編輯]

乙酰丙酮釕有 D₃ 對稱性。六個氧原子以八面體構型圍繞釕原子。乙酰丙酮釕中的Ru-O 鍵長平均為 2.00 Å。^[1]由於 Ru(acac)₃ 是低自旋的，有一個d 電子，所以是順磁性的。Ru(acac)₃ 的磁化率 χ_M為 3.032×10⁻⁶ cm³/mol，有效磁矩 μ_eff為 1.66 μ_B。^[5]在DMF溶液中，乙酰丙酮釕的氧化電位為 0.593，還原電位-1.223 V（相對於二茂鐵/二茂鐵陽離子對）。^[6]

Ru(acac)₃在烯烴存在下還原會形成二烯烴配合物。通常，此類反應是用鋅在乙醇（1,3-二烯）^[7]中或鋅汞齊在潮濕的四氫呋喃中進行的：^[8]

2 Ru(acac)₃ + 4 alkene + Zn → 2 Ru(acac)₂(alkene)₂ + Zn(acac)₂

產生的化合物是金屬烯烴配合物的罕見例子，可以可逆地維持氧化：

Ru(acac)₂(alkene)₂ ⇌ [Ru(acac)₂(alkene)₂]⁺ + e⁻

通過分離它和二苯甲酰基酒石酸的加合物，可拆分為單獨的對映異構體。^[9]

參考資料[編輯]

^ ^1.0 ^1.1 Chao, G.; Sime, R. L.; Sime, R. J. Crystal and molecular structure of tris(acetylacetonato)ruthenium(III). Acta Crystallographica B. 1973, 29 (12): 2845. doi:10.1107/S0567740873007636.
^ R.C. Mehrotra, R. Bohra, and D.P. Gaur "Metal β-Diketonates and Allied Derivatives", 1st ed.; Academic Press inc.: New York, 1978. ISBN 0-12-488150-5.
^ Barbieri, G. A. Systematic chemical investigations: ruthenium, rhodium, palladium. Atti Accad, Lincei. 1914, 23 (1): 334–40.
^ Gupta, A. Improved synthesis and reactivity of tris(acetylacetonato)ruthenium(III). Indian Journal of Chemistry, Section A. 2000, 39A (4): 457. ISSN 0376-4710.
^ Grobelny, R. The absorption spectra and magnetic properties of the chelated compounds of Ru(III) with β-diketones. Journal of Inorganic and Nuclear Chemistry. 1966, 28 (11): 2715–2718. doi:10.1016/0022-1902(66)80398-6.
^ Paul Sharpe; N. George Alameddin; David E. Richardson. Alkyl Substituent Effects in the Redox Thermochemistry of Coordination Compounds: Oxidation and Reduction Energetics for Ruthenium Tris(β-diketonate) Complexes in Solution and the Gas Phase. Journal of the American Chemical Society. 1994, 116 (24): 11098–11108. doi:10.1021/ja00103a027.
^ Richard D. Ernst, Enrique Melendez, Lothar Stahl, Manfred L. Ziegler. cis- and trans-Diene coordination in ruthenium(II) acetylacetonate compounds. Organometallics. 1991-10, 10 (10): 3635–3642 [2021-08-25]. ISSN 0276-7333. doi:10.1021/om00056a039 （英語）.
^ Bennett, M. A.; Byrnes, Matthew J.; Kováčik, Ivan. The fragment bis(acetylacetonato)ruthenium: a meeting-point of coordination and organometallic chemistry. Journal of Organometallic Chemistry. 2004, 689 (24): 4463. doi:10.1016/j.jorganchem.2004.07.027.
^ Drake, A. F.; Gould, J. M.; Mason, S. F.; Rosini, C.; Woodley, F. J. The optical resolution of tris(pentane-2,4-dionato)metal(III) complexes. Polyhedron. 1983, 2 (6): 537–538. doi:10.1016/S0277-5387(00)87108-9.

[ActaCryst-1] 1.0 ^1.1 Chao, G.; Sime, R. L.; Sime, R. J. Crystal and molecular structure of tris(acetylacetonato)ruthenium(III). Acta Crystallographica B. 1973, 29 (12): 2845. doi:10.1107/S0567740873007636.

[2] R.C. Mehrotra, R. Bohra, and D.P. Gaur "Metal β-Diketonates and Allied Derivatives", 1st ed.; Academic Press inc.: New York, 1978. ISBN 0-12-488150-5.

[3] Barbieri, G. A. Systematic chemical investigations: ruthenium, rhodium, palladium. Atti Accad, Lincei. 1914, 23 (1): 334–40.

[4] Gupta, A. Improved synthesis and reactivity of tris(acetylacetonato)ruthenium(III). Indian Journal of Chemistry, Section A. 2000, 39A (4): 457. ISSN 0376-4710.

[5] Grobelny, R. The absorption spectra and magnetic properties of the chelated compounds of Ru(III) with β-diketones. Journal of Inorganic and Nuclear Chemistry. 1966, 28 (11): 2715–2718. doi:10.1016/0022-1902(66)80398-6.

[6] Paul Sharpe; N. George Alameddin; David E. Richardson. Alkyl Substituent Effects in the Redox Thermochemistry of Coordination Compounds: Oxidation and Reduction Energetics for Ruthenium Tris(β-diketonate) Complexes in Solution and the Gas Phase. Journal of the American Chemical Society. 1994, 116 (24): 11098–11108. doi:10.1021/ja00103a027.

[7] Richard D. Ernst, Enrique Melendez, Lothar Stahl, Manfred L. Ziegler. cis- and trans-Diene coordination in ruthenium(II) acetylacetonate compounds. Organometallics. 1991-10, 10 (10): 3635–3642 [2021-08-25]. ISSN 0276-7333. doi:10.1021/om00056a039 （英語）.

[8] Bennett, M. A.; Byrnes, Matthew J.; Kováčik, Ivan. The fragment bis(acetylacetonato)ruthenium: a meeting-point of coordination and organometallic chemistry. Journal of Organometallic Chemistry. 2004, 689 (24): 4463. doi:10.1016/j.jorganchem.2004.07.027.

[9] Drake, A. F.; Gould, J. M.; Mason, S. F.; Rosini, C.; Woodley, F. J. The optical resolution of tris(pentane-2,4-dionato)metal(III) complexes. Polyhedron. 1983, 2 (6): 537–538. doi:10.1016/S0277-5387(00)87108-9.

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