乙酰丙酮钌

乙酰丙酮钌
	IUPAC名; Tris(acetylacetonato)Ruthenium (III)
别名	Ru(acac)3; 乙酰丙酮钌(III)
识别
CAS号	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;;
性质
化学式	(C5H7O2)3Ru
摩尔质量	398.39 g·mol⁻¹
外观	深紫色固体
密度	1.54 g/cm3
熔点	260 °C（533 K）
溶解性（水）	不溶
溶解性	可溶于大部分有机溶剂
危险性
警示术语	R：R36, R37, R38
安全术语	S：S26, S36
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

乙酰丙酮钌是一种乙酰丙酮配合物，化学式Ru(O₂C₅H₇)₃。它是一种深紫色固体，可溶于大多数有机溶剂。^[2]它可用来制备其它钌化合物。

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制备

1914年，乙酰丙酮钌通过三氯化钌和乙酰丙酮在碳酸氢钾下的反应首次合成。^[3]从那时起，人们已经研究了替代合成路线，但原始的制备方法仍然有用：^[4]

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

结构和性质

乙酰丙酮钌有 D₃ 对称性。六个氧原子以八面体构型围绕钌原子。乙酰丙酮钌中的Ru-O 键长平均为 2.00 Å。^[1]由于 Ru(acac)₃ 是低自旋的，有一个d 电子，所以是顺磁性的。Ru(acac)₃ 的磁化率 χ_M为 3.032×10⁻⁶ cm³/mol，有效磁矩 μ_eff为 1.66 μ_B。^[5]在DMF溶液中，乙酰丙酮钌的氧化电位为 0.593，还原电位-1.223 V（相对于二茂铁/二茂铁阳离子对）。^[6]

Ru(acac)₃在烯烃存在下还原会形成二烯烃配合物。通常，此类反应是用锌在乙醇（1,3-二烯）^[7]中或锌汞齐在潮湿的四氢呋喃中进行的：^[8]

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

产生的化合物是金属烯烃配合物的罕见例子，可以可逆地维持氧化：

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

通过分离它和二苯甲酰基酒石酸的加合物，可拆分为单独的对映异构体。^[9]

参考资料

[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 （英语）.
[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.

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

[4] [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] [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] [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] [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 （英语）.

[8] [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] [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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