Ruthenium(III) chloride is thechemical compound with the formula RuCl3. "Ruthenium(III) chloride" more commonly refers to the hydrate RuCl3·xH2O. Both the anhydrous and hydrated species are dark brown or black solids. The hydrate, with a varying proportion ofwater of crystallization, often approximating to a trihydrate, is a commonly used starting material inruthenium chemistry.
Anhydrous ruthenium(III) chloride is usually prepared by heating powdered ruthenium metal withchlorine. In the original synthesis, the chlorination was conducted in the presence ofcarbon monoxide, the product being carried by the gas stream and crystallising upon cooling.[1][2] Two polymorphs of RuCl3 are known. The black α-form adopts theCrCl3-type structure with long Ru-Ru contacts of 346pm. This polymorph has honeycomb layers of Ru3+ which are surrounded with an octahedral cage of Cl− anions. The ruthenium cations are magnetic residing in a low-spin J~1/2 ground state with net angular momentum L=1.[3][4] Layers of α-RuCl3 are stacked on top of each other with weakVan der Waals forces. These can be cleaved to form mono-layers usingscotch tape.[5]
The dark brownmetastable β-form crystallizes in a hexagonal cell; this form consists of infinite chains of face-sharing octahedra with Ru-Ru contacts of 283 pm, similar to the structure ofzirconium trichloride. The β-form is irreversibly converted to the α-form at 450–600 °C. The β-form is diamagnetic, whereas α-RuCl3 is paramagnetic at room temperature.[6]
RuCl3 vapour decomposes into theelements at high temperatures; theenthalpy change at 750 °C (1020 K), ΔdissH1020 has been estimated as +240 kJ/mol.
As the most commonly available ruthenium compound, RuCl3·xH2O is the precursor to many hundreds of chemical compounds. The noteworthy property of ruthenium complexes, chlorides and otherwise, is the existence of more than one oxidation state, several of which are kinetically inert. All second and third-row transition metals form exclusively low spin complexes, whereas ruthenium is special in the stability of adjacent oxidation states, especially Ru(II), Ru(III) (as in the parent RuCl3·xH2O) and Ru(IV).
Illustrative complexes derived from "ruthenium trichloride"
RuCl2(PPh3)3, a chocolate-colored, benzene-soluble species, which in turn is also a versatile starting material. It arises approximately as follows:[12]
Some of these compounds were utilized in the research related to twoNobel Prizes.Ryōji Noyori was awarded the Nobel Prize in Chemistry in 2001 for the development of practicalasymmetric hydrogenation catalysts based on ruthenium.Robert H. Grubbs was awarded the Nobel Prize in Chemistry in 2005 for the development of practicalalkene metathesis catalysts based on rutheniumalkylidene derivatives.
RuCl3(H2O)x reacts with carbon monoxide under mild conditions.[18] In contrast,iron chlorides do not react with CO. CO reduces the red-brown trichloride to yellowish Ru(II) species. Specifically, exposure of anethanol solution of RuCl3(H2O)x to 1 atm of CO gives, depending on the specific conditions, [Ru2Cl4(CO)4], [Ru2Cl4(CO)4]2−, and [RuCl3(CO)3]−. Addition of ligands (L) to such solutions gives Ru-Cl-CO-L compounds (L = PR3). Reduction of these carbonylated solutions with Zn affords the orange triangular clusterRu3(CO)12.
^Remy, H.; Kühn, M. (1924). "Beiträge zur Chemie der Platinmetalle. V. Thermischer Abbau des Ruthentrichlorids und des Ruthendioxyds".Z. Anorg. Allg. Chem.137 (1):365–388.doi:10.1002/zaac.19241370127.
^Bublitz, D. E; McEwen, W. E.; Kleinberg, J. (1961). "Ruthenocene".Organic Syntheses.41: 96.doi:10.15227/orgsyn.041.0096.
^Zhou, Boyi; Wang, Yiping; Osterhoudt, Gavin B.; Lampen-Kelley, Paula; Mandrus, David; He, Rui; Burch, Kenneth S.; Henriksen, Erik A. (2019). "Possible Structural Transformation and Enhanced Magnetic Fluctuations in Exfoliated αRuCl3".Journal of Physics and Chemistry of Solids.128:291–295.arXiv:1709.00431.Bibcode:2019JPCS..128..291Z.doi:10.1016/j.jpcs.2018.01.026.ISSN0022-3697.S2CID103743571.
^Fletcher, J. M.; Gardner, W. E.; Fox, A. C.; Topping, G. (1967). "X-Ray, infrared, and magnetic studies of α- and β-ruthenium trichloride".Journal of the Chemical Society A: Inorganic, Physical, Theoretical:1038–1045.doi:10.1039/J19670001038.
^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
^Kölle, Urich; Kossakowski, Janusz (1992).Di-μ-Chloro-Bis[(η5-Pentamethylcyclopentadienyl) Chlororuthenium(III)], [Cp*RuCl2]2 and Di-μ-methoxo-Bis(η5-Pentamethylcyclopentadienyl)diruthenium(II), [Cp*RuOMe]2. Inorganic Syntheses. Vol. 29. pp. 225–228.doi:10.1002/9780470132609.ch52.ISBN978-0-470-13260-9.
^Gupta, A. (2000). "Improved synthesis and reactivity of tris(acetylacetonato)ruthenium(III)".Indian Journal of Chemistry, Section A.39A (4): 457.ISSN0376-4710.
Carlsen, P. H. J.; Martin, Victor S.; et al. (1981). "A greatly improved procedure for ruthenium tetroxide catalyzed oxidations of organic compounds".J. Org. Chem.46 (19): 3936.doi:10.1021/jo00332a045.
