Ruthenium(III) chloride

Ruthenium(III) chloride is the chemical 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 of water of crystallization, often approximating to a trihydrate, is a commonly used starting material in ruthenium chemistry.

Ruthenium(III) chloride

Identifiers
CAS Number	10049-08-8 Y 13815-94-6 (trihydrate) N 14898-67-0 (x-hydrate) N
3D model (JSmol)	Interactive image Interactive image
ChemSpider	74294 Y
ECHA InfoCard	100.030.139
PubChem CID	82323
RTECS number	VM2650000
UNII	RY8V1UJV23 Y
CompTox Dashboard (EPA)	DTXSID101014308 DTXSID00275675, DTXSID101014308
InChI InChI=1S/3ClH.Ru/h3*1H;/q;;;+3/p-3 Y Key: YBCAZPLXEGKKFM-UHFFFAOYSA-K Y InChI=1/3ClH.Ru/h3*1H;/q;;;+3/p-3 Key: YBCAZPLXEGKKFM-DFZHHIFOAX
SMILES Cl[Ru](Cl)Cl [Cl-].[Cl-].[Cl-].[Ru+3]
Properties
Chemical formula	RuCl3·xH2O
Molar mass	207.43 g/mol
Melting point	>500°C (decomposes)
Solubility in water	Soluble, Anhydrous is insoluble
Magnetic susceptibility (χ)	+1998.0·10−6 cm3/mol
Structure
Crystal structure	trigonal (RuCl3), hP8
Space group	P3c1, No. 158
Coordination geometry	octahedral
Hazards
Flash point	Nonflammable
Related compounds
Other anions	Ruthenium(III) bromide
Other cations	Rhodium(III) chloride Iron(III) chloride
Related compounds	Ruthenium tetroxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). N verify (what is YN ?) Infobox references

Preparation and properties

Anhydrous ruthenium(III) chloride is usually prepared by heating powdered ruthenium metal with chlorine. In the original synthesis, the chlorination was conducted in the presence of carbon 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 the CrCl₃-type structure with long Ru-Ru contacts of 346 pm. 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 weak Van der Waals forces. These can be cleaved to form mono-layers using scotch tape.^[5]

The dark brown metastable 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 of zirconium 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 the elements at high temperatures ; the enthalpy change at 750 °C (1020 K), Δ_dissH₁₀₂₀ has been estimated as +240 kJ/mol.

Solid state physics

α-RuCl₃ was proposed as a candidate for a Kitaev quantum spin liquid state^[7] when neutron scattering revealed an unusual magnetic spectrum,^[8][9][10] and thermal transport revealed chiral Majorana Fermions when subject to a magnetic field.^[11]

Coordination chemistry of hydrated ruthenium trichloride

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]

2 RuCl₃·xH₂O + 7 PPh₃ → 2 RuCl₂(PPh₃)₃ + OPPh₃ + 5 H₂O + 2 HCl

• Diruthenium tetraacetate chloride, a mixed valence polymer, is obtained by reduction of ruthenium trichloride in acetic acid.
• [RuCl₂(C₆H₆)]₂ arises from 1,3-cyclohexadiene or 1,4-cyclohexadiene as follows:^[13][14]

2 RuCl₃·xH₂O + 2 C₆H₈ → [RuCl₂(C₆H₆)]₂ + 6 H₂O + 2 HCl + H₂

• Ru(bipy)₃Cl₂, an intensely luminescent salt with a long-lived excited state, arising as follows:^[15]

2 RuCl₃·xH₂O + 6 bipy + CH₃CH₂OH → 2 [Ru(bipy)₃]Cl₂ + 6 H₂O + CH₃CHO + 2 HCl

This reaction proceeds via the intermediate cis-Ru(bipy)₂Cl₂.^[15]

• [RuCl₂(C₅Me₅)]₂, arising as follows:^[16]

2 RuCl₃·xH₂O + 2 C₅Me₅H → [RuCl₂(C₅Me₅)]₂ + 6 H₂O + 2 HCl

[RuCl₂(C₅Me₅)]₂ can be further reduced to [RuCl(C₅Me₅)]₄.

• Ru(C₅H₇O₂)₃ arises as follows:^[17]

RuCl₃·xH₂O + 3 C₅H₈O₂ → Ru(C₅H₇O₂)₃ + 3 H₂O + 3 HCl

• RuO₄, is produced by oxidation.

Some of these compounds were utilized in the research related to two Nobel Prizes. Ryōji Noyori was awarded the Nobel Prize in Chemistry in 2001 for the development of practical asymmetric hydrogenation catalysts based on ruthenium. Robert H. Grubbs was awarded the Nobel Prize in Chemistry in 2005 for the development of practical alkene metathesis catalysts based on ruthenium alkylidene derivatives.

Carbon monoxide 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 an ethanol 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 cluster Ru₃(CO)₁₂.

3 RuCl₃·xH₂O + 4.5 Zn + 12 CO (high pressure) → Ru₃(CO)₁₂ + 3x H₂O + 4.5 ZnCl₂

Sources

• Becker, Ramona; Hartwig, Helga; Köppe, Herbert; Vanecek, Hans; Velić, Paul; Warncke, Rudolf; Zelle, Anna (1978). Warncke, Rudolf (ed.). Gmelin Handbuch der Anorganischen Chemie. doi:10.1007/978-3-662-06224-1. ISBN 978-3-662-06226-5.

References

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2. Bublitz, D. E; McEwen, W. E.; Kleinberg, J. (1961). "Ruthenocene". Organic Syntheses. 41: 96. doi:10.15227/orgsyn.041.0096.
3. Fletcher, J. M.; Gardner, W. E.; Hooper, E. W.; Hyde, K. R.; Moore, F. H.; Woodhead, J. L. (September 1963). "Anhydrous Ruthenium Chlorides". Nature. 199 (4898): 1089–1090. Bibcode:1963Natur.199.1089F. doi:10.1038/1991089a0. ISSN 0028-0836. S2CID 4179795.
4. Plumb, K. W.; Clancy, J. P.; Sandilands, L. J.; Shankar, V. Vijay; Hu, Y. F.; Burch, K. S.; Kee, Hae-Young; Kim, Young-June (2014-07-29). "α−RuCl₃: A Spin-Orbit Assisted Mott Insulator on a Honeycomb Lattice". Physical Review B. 90 (4): 041112. arXiv:1403.0883. Bibcode:2014PhRvB..90d1112P. doi:10.1103/physrevb.90.041112. ISSN 1098-0121. S2CID 29688091.
5. 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. ISSN 0022-3697. S2CID 103743571.
6. 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.
7. Banerjee, A.; Bridges, C. A.; Yan, J.-Q.; Aczel, A. A.; Li, L.; Stone, M. B.; Granroth, G. E.; Lumsden, M. D.; Yiu, Y. (2016-04-04). "Proximate Kitaev quantum spin liquid behaviour in a honeycomb magnet". Nature Materials. 15 (7): 733–740. arXiv:1504.08037. Bibcode:2016NatMa..15..733B. doi:10.1038/nmat4604. ISSN 1476-1122. PMID 27043779. S2CID 3406627.
8. Banerjee, Arnab; Yan, Jiaqiang; Knolle, Johannes; Bridges, Craig A.; Stone, Matthew B.; Lumsden, Mark D.; Mandrus, David G.; Tennant, David A.; Moessner, Roderich (2017-06-09). "Neutron scattering in the proximate quantum spin liquid α-RuCl 3". Science. 356 (6342): 1055–1059. arXiv:1609.00103. Bibcode:2017Sci...356.1055B. doi:10.1126/science.aah6015. ISSN 0036-8075. PMID 28596361. S2CID 206652434.
9. Do, Seung-Hwan; Park, Sang-Youn; Yoshitake, Junki; Nasu, Joji; Motome, Yukitoshi; Kwon, Yong Seung; Adroja, D. T.; Voneshen, D. J.; Kim, Kyoo (2017-09-18). "Majorana fermions in the Kitaev quantum spin system α-RuCl3". Nature Physics. 13 (11): 1079–1084. Bibcode:2017NatPh..13.1079D. doi:10.1038/nphys4264. ISSN 1745-2473. S2CID 126423385.
10. Banerjee, Arnab; Lampen-Kelley, Paula; Knolle, Johannes; Balz, Christian; Aczel, Adam Anthony; Winn, Barry; Liu, Yaohua; Pajerowski, Daniel; Yan, Jiaqiang; Bridges, Craig A.; Savici, Andrei T.; Chakoumakos, Bryan C.; Lumsden, Mark D.; Tennant, David Alan; Moessner, Roderich; Mandrus, David G.; Nagler, Stephen E. (2018-02-20). "Excitations in the field-induced quantum spin liquid state of α-RuCl 3". npj Quantum Materials. 3 (1): 8. arXiv:1706.07003. Bibcode:2018npjQM...3....8B. doi:10.1038/s41535-018-0079-2. ISSN 2397-4648. S2CID 55484993.
11. Kasahara, Y.; Ohnishi, T.; Mizukami, Y.; Tanaka, O.; Ma, Sixiao; Sugii, K.; Kurita, N.; Tanaka, H.; Nasu, J. (July 2018). "Majorana quantization and half-integer thermal quantum Hall effect in a Kitaev spin liquid". Nature. 559 (7713): 227–231. arXiv:1805.05022. Bibcode:2018Natur.559..227K. doi:10.1038/s41586-018-0274-0. ISSN 0028-0836. PMID 29995863. S2CID 49664700.
12. 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
13. Bennett, Martin A.; Smith, Anthony K. (1974-01-01). "Arene ruthenium(II) complexes formed by dehydrogenation of cyclohexadienes with ruthenium(III) trichloride". Journal of the Chemical Society, Dalton Transactions (2): 233–241. doi:10.1039/dt9740000233. ISSN 1364-5447.
14. Bennett, M. A.; Huang, T. N.; Matheson, T. W. & Smith, A. K. (1982). (η⁶-Hexamethylbenzene)ruthenium Complexes. Inorganic Syntheses. Vol. 21. pp. 74–8. doi:10.1002/9780470132524.ch16. ISBN 9780470132524.
15. Broomhead, J. A.; Young, C. G. (1990). Tris(2,2'-bipyridine)Ruthenium(II) Dichloride Hexahydrate. Inorganic Syntheses. Vol. 28. pp. 338–340. doi:10.1002/9780470132593.ch86. ISBN 9780470132593.
16. 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. ISBN 9780470132609.
17. Gupta, A. (2000). "Improved synthesis and reactivity of tris(acetylacetonato)ruthenium(III)". Indian Journal of Chemistry, Section A. 39A (4): 457. ISSN 0376-4710.
18. Hill, A. F. (2000). ""Simple" Ruthenium Carbonyls of Ruthenium: New Avenues from the Hieber Base Reaction". Angew. Chem. Int. Ed. 39 (1): 130–134. doi:10.1002/(SICI)1521-3773(20000103)39:1<130::AID-ANIE130>3.0.CO;2-6. PMID 10649352.

Further reading

• 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.
• Cotton, S. A. (1997). Chemistry of Precious Metals. doi:10.1007/978-94-009-1463-6. ISBN 0-7514-0413-6.
• Ikariya, Takao; Murata, Kunihiko; Noyori, Ryoji (2006). "Bifunctional transition metal-based molecular catalysts for asymmetric syntheses". Org. Biomol. Chem. 4 (3): 393–406. doi:10.1039/B513564H. PMID 16446796. S2CID 29116338.