二氯三(三苯基膦)钌(II)

二氯三(三苯基膦)钌(II)
	IUPAC名; Dichlorotris(triphenylphosphine)ruthenium(II)
别名	Ruthenium tris(triphenylphosphine) dichloride; Tris(triphenylphosphine)dichlororuthenium; Tris(triphenylphosphine)ruthenium dichloride;Tris(triphenylphosphine)ruthenium(II) dichloride
识别
CAS号	15529-49-4
PubChem	11007548
ChemSpider	76650
SMILES	[Ru+2].[Cl-].[Cl-].c3c(P(c1ccccc1)c2ccccc2)cccc3.c1ccccc1P(c2ccccc2)c3ccccc3.c1ccccc1P(c2ccccc2)c3ccccc3;
InChI	1/3C18H15P.2ClH.Ru/c31-4-10-16(11-5-1)19(17-12-6-2-7-13-17)18-14-8-3-9-15-18;;;/h31-15H;2*1H;/q;;;;;+2/p-2;
InChIKey	WIWBLJMBLGWSIN-NUQVWONBAX
EINECS	239-569-7
性质
化学式	C54H45Cl2P3Ru
摩尔质量	958.83 g/mol g·mol⁻¹
外观	黑色或红棕色晶体
密度	1.43 g cm−3
熔点	133 °C（406 K）
结构
晶体结构	单斜晶系
空间群	C2h5-P21/c
晶格常数	a = 18.01 Å, b = 20.22 Å, c = 12.36 Å
晶格常数	α = 90°, β = 90.5°, γ = 90°
配位几何	八面体
危险性
	GHS危险性符号;
GHS提示词	Warning
H-术语	H302, H312, H332
P-术语	P261, P264, P270, P271, P280, P301+312, P302+352, P304+312, P304+340, P312, P322, P330, P363, P501
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

二氯三(三苯基膦)钌(II)是钌的一个配位化合物。它是棕色固体，可溶于诸如苯的有机溶剂。它是其他配合物（包括均相催化所用的配合物）的合成前体。

合成和基本性质

RuCl₂(PPh₃)₃由三水合三氯化钌与三苯基膦的甲醇溶液反应而成。^[1]^[2]

2 RuCl₃(H₂O)₃ + 7 PPh₃ → 2 RuCl₂(PPh₃)₃ + 2 HCl + 5 H₂O + OPPh₃

RuCl₂(PPh₃)₃为五配体配合物，配位域呈八面体形，其中有一个配位位点被苯基的一个氢原子占有。^[3]Ru-H抓氢键长（2.59 Å）而弱。由Ru-P键长的差异（2.374 Å、2.412 Å和2.230 Å）可见，这个化合物不太对称。^[4]Ru-Cl键长都是2.387 Å。

反应

RuCl₂(PPh₃)₃在过量三苯基膦中会与第四个膦结合，生成黑色的RuCl₂(PPh₃)₄。三膦和四膦配合物中的三苯基膦配体可容易替代为其他配体。四膦配合物是格拉布催化剂的合成前体。^[5]

二氯三(三苯基膦)钌(II)在碱性环境中能与氢反应，生成紫色的HRuCl(PPh₃)₃一氢化物。^[6]

RuCl₂(PPh₃)₃ + H₂ + NEt₃ → HRuCl(PPh₃)₃ + [HNEt₃]Cl

二氯三(三苯基膦)钌(II)与一氧化碳反应，形成二氯二羰基三(三苯基膦)钌(II)的所有反式异构体。

RuCl₂(PPh₃)₃ + 2 CO → trans,trans,trans-RuCl₂(CO)₂(PPh₃)₂ + PPh₃

这个生成物在重结晶时会异构化成顺式加成物。用1,2-双(二苯基膦)乙烷处理RuCl₂(PPh₃)₃后，会形成trans-RuCl₂(dppe)₂。

RuCl₂(PPh₃)₃ + 2 dppe → RuCl₂(dppe)₂ + 3 PPh₃

RuCl₂(PPh₃)₃能催化甲酸在胺的存在下分解成二氧化碳和氢气的反应。^[7]

有机合成的用途

RuCl₂(PPh₃)₃能催化氧化反应、还原反应、交叉偶联反应、环化反应和异构化反应。它用于氯烃与烯的卡拉施加成反应（英语：Kharasch addition）。^[8]

二氯三(三苯基膦)钌(II)是烯、硝基化合物、酮、羧酸和亚胺的氢化反应的催化剂前体。此外，在过氧化叔丁醇的存在下，它也能催化烷、酰胺和叔胺的氧化反应，分别生成叔醇、t-丁基二氧代酰胺和α-(t-丁基二氧代酰胺)。在其他过氧化物、氧和丙酮的存在下，RuCl₂(PPh₃)₃能将醇氧化成醛或酮。二氯三(三苯基膦)钌(II)也能催化胺与醇的N-烷基化。^[8]

在路易斯酸的存在下，RuCl₂(PPh₃)₃可以通过sp³碳原子的C-H活化反应高效催化醇的交叉偶联反应，形成碳-碳键。^[9]

参考文献

^ Stephenson, T. A.; Wilkinson, G. "New Complexes of Ruthenium (II) and (III) with Triphenylphosphine, Triphenylarsine, Trichlorostannate, Pyridine, and other Ligands", J. Inorg. Nucl. Chem., 1966, 28, 945-956. doi:10.1016/0022-1902(66)80191-4
^ P. S. Hallman, T. A. Stephenson, G. Wilkinson "Tetrakis(Triphenylphosphine)Dichloro-Ruthenium(II) and Tris(Triphenylphosphine)-Dichlororuthenium(II)" Inorganic Syntheses, 1970 volume 12 doi:10.1002/9780470132432.ch40
^ Sabo-Etienne, Sylviane; Grellier, Mary. Ruthenium: Inorganic & Coordination Chemistry Based in part on the article Ruthenium: Inorganic & Coordination Chemistry by Bruno Chaudret & Sylviane Sabo-Etienne which appeared in the Encyclopedia of Inorganic Chemistry, First Edition. Encyclopedia of Inorganic Chemistry. 2006. ISBN 0470860782. doi:10.1002/0470862106.ia208.
^ La Placa, Sam J.; Ibers, James A. A Five-Coordinated d6 Complex: Structure of Dichlorotris(triphenylphosphine)ruthenium (II). Inorganic Chemistry. 1965, 4 (6): 778–783. doi:10.1021/ic50028a002.
^ Vougioukalakis, Georgios C.; Grubbs, Robert H. Ruthenium-Based Heterocyclic Carbene-Coordinated Olefin Metathesis Catalysts. Chemical Reviews. 2010, 110 (3): 1746–1787. PMID 20000700. doi:10.1021/cr9002424.
^ Schunn, R. A.; Wonchoba, E. R. Chlorohydridotris(triphenylphosphine)ruthenium(II). Inorganic Syntheses 13. 1972: 131. ISBN 9780470132449. doi:10.1002/9780470132449.ch26.
^ Loges, Björn; Boddien, Albert; Junge, Henrik; Beller, Matthias. Controlled Generation of Hydrogen from Formic Acid Amine Adducts at Room Temperature and Application in H2/O2Fuel Cells. Angewandte Chemie International Edition. 2008, 47 (21): 3962–3965. PMID 18457345. doi:10.1002/anie.200705972.
^ ^8.0 ^8.1 Plummer, J. S.; Shun-Ichi, M.; Changjia, Z. "Dichlorotris(triphenylphosphine)ruthenium(II)", e-EROS Encyclopedia of Reagents for Organic Synthesis, 2010, John Wiley doi:10.1002/047084289X.rd137.pub2
^ Zhang, Shu-Yu; Tu, Yong-Qiang; Fan, Chun-An; Jiang, Yi-Jun; Shi, Lei; Cao, Ke; Zhang, En. Cross-Coupling Reaction between Alcohols through sp³ C−H Activation Catalyzed by a Ruthenium/Lewis Acid System. Chemistry - A European Journal. 2008, 14 (33): 10201–10205. PMID 18844197. doi:10.1002/chem.200801317.

[1] Stephenson, T. A.; Wilkinson, G. "New Complexes of Ruthenium (II) and (III) with Triphenylphosphine, Triphenylarsine, Trichlorostannate, Pyridine, and other Ligands", J. Inorg. Nucl. Chem., 1966, 28, 945-956. doi:10.1016/0022-1902(66)80191-4

[2] P. S. Hallman, T. A. Stephenson, G. Wilkinson "Tetrakis(Triphenylphosphine)Dichloro-Ruthenium(II) and Tris(Triphenylphosphine)-Dichlororuthenium(II)" Inorganic Syntheses, 1970 volume 12 doi:10.1002/9780470132432.ch40

[3] Sabo-Etienne, Sylviane; Grellier, Mary. Ruthenium: Inorganic & Coordination Chemistry Based in part on the article Ruthenium: Inorganic & Coordination Chemistry by Bruno Chaudret & Sylviane Sabo-Etienne which appeared in the Encyclopedia of Inorganic Chemistry, First Edition. Encyclopedia of Inorganic Chemistry. 2006. ISBN 0470860782. doi:10.1002/0470862106.ia208.

[4] La Placa, Sam J.; Ibers, James A. A Five-Coordinated d6 Complex: Structure of Dichlorotris(triphenylphosphine)ruthenium (II). Inorganic Chemistry. 1965, 4 (6): 778–783. doi:10.1021/ic50028a002.

[5] Vougioukalakis, Georgios C.; Grubbs, Robert H. Ruthenium-Based Heterocyclic Carbene-Coordinated Olefin Metathesis Catalysts. Chemical Reviews. 2010, 110 (3): 1746–1787. PMID 20000700. doi:10.1021/cr9002424.

[6] Schunn, R. A.; Wonchoba, E. R. Chlorohydridotris(triphenylphosphine)ruthenium(II). Inorganic Syntheses 13. 1972: 131. ISBN 9780470132449. doi:10.1002/9780470132449.ch26.

[7] Loges, Björn; Boddien, Albert; Junge, Henrik; Beller, Matthias. Controlled Generation of Hydrogen from Formic Acid Amine Adducts at Room Temperature and Application in H2/O2Fuel Cells. Angewandte Chemie International Edition. 2008, 47 (21): 3962–3965. PMID 18457345. doi:10.1002/anie.200705972.

[eEROS-8] 8.0 ^8.1 Plummer, J. S.; Shun-Ichi, M.; Changjia, Z. "Dichlorotris(triphenylphosphine)ruthenium(II)", e-EROS Encyclopedia of Reagents for Organic Synthesis, 2010, John Wiley doi:10.1002/047084289X.rd137.pub2

[9] Zhang, Shu-Yu; Tu, Yong-Qiang; Fan, Chun-An; Jiang, Yi-Jun; Shi, Lei; Cao, Ke; Zhang, En. Cross-Coupling Reaction between Alcohols through sp³ C−H Activation Catalyzed by a Ruthenium/Lewis Acid System. Chemistry - A European Journal. 2008, 14 (33): 10201–10205. PMID 18844197. doi:10.1002/chem.200801317.

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