三氟乙酸铑(II)

三氟乙酸铑(II)
别名	三氟乙酸铑(II)二聚体; 四(μ-三氟乙酸根)合二铑; 四(三氟乙酸)二铑
识别
CAS号	31126-95-1（无水） ; 70084-34-3（二水）
PubChem	10985187
ChemSpider	380904
SMILES	C(=O)(C(F)(F)F)O.C(=O)(C(F)(F)F)O.C(=O)(C(F)(F)F)O.C(=O)(C(F)(F)F)O.[Rh].[Rh];
性质
化学式	C8F12O8Rh2
摩尔质量	657.87 g·mol−1
外观	翠绿色针状晶体（无水）; 蓝色（水合物）
密度	2.750 g·cm−3（−60 °C，无水）; 2.292 g·cm−3（20 °C，二水）
沸点	260 °C（~10−2 Torr）（升华）
危险性
	GHS危险性符号;
GHS提示词	警告
H-术语	H315, H319, H335
P-术语	P261, P264, P271, P280, P302+352, P305+351+338
主要危害	特定目标器官毒性3级（STOT-SE-3）：; 皮肤刺激-2; 眼刺激-2
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

三氟乙酸铑(II)是一种无机化合物，化学式为Rh
2(O
2CCF
3)
4。它可用作一些有机反应的催化剂。^[2]其单晶数据通过石墨单色化的Mo靶X射线衍射收集、结构经数据处理后得到。它和其它M₂羧酸根配合物一样，具有中国灯笼结构，该分子中存在Rh-Rh键，键长为2.38 Å。^[1]

合成

三氟乙酸铑(II)可由乙酸铑(II)和热的三氟乙酸反应制得：^[5]

Rh
2(O
2CCH
3)
4 + 4 HO
2CCF
3 → Rh
2(O
2CCF
3)
4 + 4 HO
2CCH
3

反应

三氟乙酸铑(II)常以2:1的计量比和一系列的路易斯碱形成加合物，路易斯碱在Rh(II)中心的轴向位置与之键合：

Rh
2(O
2CCF
3)
4 + 2 L → Rh
2(O
2CCF
3)
4L
2 (L = CO, RCN, R₂SO, R₃P, ...)

它也可以和很弱的碱（如六甲苯或S₈）形成加合物。^[6]

它和不同配体（L）形成的加合物（Rh₂(O₂CCF₃)₄·2L）的颜色不同，配体为水、三乙胺、吡啶、三苯基膦和二乙硫醚时，分别为蓝色、玫瑰红色、橙红色、橙黄色和玫瑰红色；^[7]Rh₂(O₂CCF₃)₄S₈和[Rh₂(O₂CCF₃)₄]₃(S₈)₂为暗紫色晶体。^[6]

应用

三氟乙酸铑(II)可用于催化偶氮基团的一些有机转化，例如：^[8]

它的二水合物（Rh₂(O₂CCF₃)₄(H₂O)₂）可用于催化光化学析氢反应。^[9]

参考文献

^ ^1.0 ^1.1 ^1.2 ^1.3 Cotton, F. Albert; Dikarev, Evgeny V.; Feng, Xuejun. Unligated Dirhodium Tetra(trifluoroacetate): Preparation, Crystal Structure and Electronic Structure. Inorganica Chimica Acta. 1995, 237 (1–2): 19–26. doi:10.1016/0020-1693(95)04662-S.
^ ^2.0 ^2.1 Doyle, Michael P.; Davies, Huw M. L.; Manning, James R.; Yu, Yang. Dirhodium(II) tetrakis(trifluoroacetate). EEROS. 2018. doi:10.1002/047084289X.rd461.pub3.
^ Cotton, F. A.; Kim, Y. Three Rh2(O2CCF3)4L2 compounds, with L = H2O, tetrahydrofuran and acetonitrile. European Journal of Solid State and Inorganic Chemistry. 1994, 31: 525-534.
^ Rhodium(II) trifluoroacetate dimer. SigmaAldrich. [2024-07-08].
^ Felthouse, Timothy R. The Chemistry, Structure, and Metal-Metal Bonding in Compounds of Rhodium(II). Progress in Inorganic Chemistry 29. 1982: 73–166. ISBN 978-0-471-09370-1. doi:10.1002/9780470166307.ch2.
^ ^6.0 ^6.1 Cotton, F. Albert; Dikarev, Evgeny V.; Petrukhina, Marina A. Neutral Cyclooctasulfur as a Polydentate Ligand: Supramolecular Structures of [Rh2(O2CCF3)4]n(S8)m (N:m=1:1, 3:2). Angewandte Chemie International Edition. 2001, 40 (8): 1521–1523. doi:10.1002/1521-3773(20010417)40:8<1521::AID-ANIE1521>3.0.CO;2-M.
^ Judith Kitchens; John L. Bear. The thermal decomposition of some rhodium(II) carboxylate complexes. Thermochim. Acta. 1970, 1 (6): 537–544. doi:10.1016/0040-6031(70)80005-3.
^ Jiawen Chen; Ying Shao; Shengbiao Tang; Jiangtao Sun. Enantioselective insertion of vinyl diazoacetates into O–H bonds of carboxylic acids. New Journal of Chemistry. 2024, 48: 5092-5096. doi:10.1039/D4NJ00289J.
^ Kataoka, Yusuke; Yano, Natsumi; Kohara, Yoshihiro; Tsuji, Takeshi; Inoue, Satoshi; Kawamoto, Tatsuya. Experimental and Theoretical Study of Photochemical Hydrogen Evolution Catalyzed by Paddlewheel‐Type Dirhodium Complexes with Electron Withdrawing Carboxylate Ligands. ChemCatChem. 2019, 11: 1–10. doi:10.1002/cctc.201901534.

[Cotton-1] 1.0 ^1.1 ^1.2 ^1.3 Cotton, F. Albert; Dikarev, Evgeny V.; Feng, Xuejun. Unligated Dirhodium Tetra(trifluoroacetate): Preparation, Crystal Structure and Electronic Structure. Inorganica Chimica Acta. 1995, 237 (1–2): 19–26. doi:10.1016/0020-1693(95)04662-S.

[Rh2-2] 2.0 ^2.1 Doyle, Michael P.; Davies, Huw M. L.; Manning, James R.; Yu, Yang. Dirhodium(II) tetrakis(trifluoroacetate). EEROS. 2018. doi:10.1002/047084289X.rd461.pub3.

[3] Cotton, F. A.; Kim, Y. Three Rh2(O2CCF3)4L2 compounds, with L = H2O, tetrahydrofuran and acetonitrile. European Journal of Solid State and Inorganic Chemistry. 1994, 31: 525-534.

[4] Rhodium(II) trifluoroacetate dimer. SigmaAldrich. [2024-07-08].

[5] Felthouse, Timothy R. The Chemistry, Structure, and Metal-Metal Bonding in Compounds of Rhodium(II). Progress in Inorganic Chemistry 29. 1982: 73–166. ISBN 978-0-471-09370-1. doi:10.1002/9780470166307.ch2.

[Angew-6] 6.0 ^6.1 Cotton, F. Albert; Dikarev, Evgeny V.; Petrukhina, Marina A. Neutral Cyclooctasulfur as a Polydentate Ligand: Supramolecular Structures of [Rh2(O2CCF3)4]n(S8)m (N:m=1:1, 3:2). Angewandte Chemie International Edition. 2001, 40 (8): 1521–1523. doi:10.1002/1521-3773(20010417)40:8<1521::AID-ANIE1521>3.0.CO;2-M.

[7] Judith Kitchens; John L. Bear. The thermal decomposition of some rhodium(II) carboxylate complexes. Thermochim. Acta. 1970, 1 (6): 537–544. doi:10.1016/0040-6031(70)80005-3.

[8] Jiawen Chen; Ying Shao; Shengbiao Tang; Jiangtao Sun. Enantioselective insertion of vinyl diazoacetates into O–H bonds of carboxylic acids. New Journal of Chemistry. 2024, 48: 5092-5096. doi:10.1039/D4NJ00289J.

[9] Kataoka, Yusuke; Yano, Natsumi; Kohara, Yoshihiro; Tsuji, Takeshi; Inoue, Satoshi; Kawamoto, Tatsuya. Experimental and Theoretical Study of Photochemical Hydrogen Evolution Catalyzed by Paddlewheel‐Type Dirhodium Complexes with Electron Withdrawing Carboxylate Ligands. ChemCatChem. 2019, 11: 1–10. doi:10.1002/cctc.201901534.

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