二氯三(三苯基膦)釕(II)

二氯三(三苯基膦)釕(II)
	IUPAC名; Dichlorotris(triphenylphosphine)ruthenium(II)
別名	Ruthenium tris(triphenylphosphine) dichloride; Tris(triphenylphosphine)dichlororuthenium; Tris(triphenylphosphine)ruthenium dichloride;Tris(triphenylphosphine)ruthenium(II) dichloride
識別
CAS號	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
性質
化學式	C54H45Cl2P3Ru
摩爾質量	958.83 g/mol g·mol⁻¹
外觀	黑色或紅棕色晶體
密度	1.43 g cm−3
熔點	133 °C（406 K）
結構
晶體結構	單斜晶系
空間群	C2h5-P21/c
晶格常數	a = 18.01 Å, b = 20.22 Å, c = 12.36 Å
晶格常數	α = 90°, β = 90.5°, γ = 90°
配位幾何	八面體
危險性
	GHS危險性符號;
GHS提示詞	Warning
H-術語	H302, H312, H332
P-術語	P261, P264, P270, P271, P280, P301+312, P302+352, P304+312, P304+340, P312, P322, P330, P363, P501
	若非註明，所有數據均出自標準狀態（25 ℃，100 kPa）下。

二氯三(三苯基膦)釕(II)是釕的一個配位化合物。它是棕色固體，可溶於諸如苯的有機溶劑。它是其他配合物（包括均相催化所用的配合物）的合成前體。

合成和基本性質

RuCl₂(PPh₃)₃由三水合三氯化釕與三苯基膦的甲醇溶液反應而成。^[1]^[2]

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

RuCl₂(PPh₃)₃為五配體配合物，配位域呈八面體形，其中有一個配位位點被苯基的一個氫原子占有。^[3]Ru-H抓氫鍵長（2.59 Å）而弱。由Ru-P鍵長的差異（2.374 Å、2.412 Å和2.230 Å）可見，這個化合物不太對稱。^[4]Ru-Cl鍵長都是2.387 Å。

反應

RuCl₂(PPh₃)₃在過量三苯基膦中會與第四個膦結合，生成黑色的RuCl₂(PPh₃)₄。三膦和四膦配合物中的三苯基膦配體可容易替代為其他配體。四膦配合物是格拉布催化劑的合成前體。^[5]

二氯三(三苯基膦)釕(II)在鹼性環境中能與氫反應，生成紫色的HRuCl(PPh₃)₃一氫化物。^[6]

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

二氯三(三苯基膦)釕(II)與一氧化碳反應，形成二氯二羰基三(三苯基膦)釕(II)的所有反式異構體。

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

這個生成物在重結晶時會異構化成順式加成物。用1,2-雙(二苯基膦)乙烷處理RuCl₂(PPh₃)₃後，會形成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氫氣的反應。^[7]

有機合成的用途

RuCl₂(PPh₃)₃能催化氧化反應、還原反應、交叉偶聯反應、環化反應和異構化反應。它用於氯烴與烯的卡拉施加成反應（英語：Kharasch addition）。^[8]

二氯三(三苯基膦)釕(II)是烯、硝基化合物、酮、羧酸和亞胺的氫化反應的催化劑前體。此外，在過氧化叔丁醇的存在下，它也能催化烷、酰胺和三級胺的氧化反應，分別生成三級醇、t-丁基二氧代酰胺和α-(t-丁基二氧代酰胺)。在其他過氧化物、氧和丙酮的存在下，RuCl₂(PPh₃)₃能將醇氧化成醛或酮。二氯三(三苯基膦)釕(II)也能催化胺與醇的N-烷基化。^[8]

在路易斯酸的存在下，RuCl₂(PPh₃)₃可以通過sp³碳原子的C-H活化反應高效催化醇的交叉偶聯反應，形成碳-碳鍵。^[9]

參考文獻

^ 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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