Nitrosylruthenium(II) nitrate
| Names | |
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| IUPAC name
azanylidyneoxidanium;ruthenium(2+);trinitrate | |
Other names
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| Identifiers | |
3D model (JSmol) |
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| ChemSpider | |
| ECHA InfoCard | 100.047.320 |
| EC Number |
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PubChem CID |
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CompTox Dashboard (EPA) |
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| Properties | |
| Ru(NO)(NO3)3 | |
| Molar mass | 317.09 g/mol |
| Appearance | Red-brown solid |
| Soluble, slow hydrolysis[1] | |
| Solubility | Soluble in nitric acid and various organic solvents[1] |
| Hazards | |
| GHS labelling:[2] | |
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| Danger | |
| H271, H290, H314, H411 | |
| P210, P220, P234, P260, P264, P264+P265, P273, P280, P283, P301+P330+P331, P302+P361+P354, P304+P340, P305+P354+P338, P306+P360, P316, P317, P321, P363, P370+P378, P371+P380+P375, P390, P391, P405, P420, P501 | |
| NFPA 704 (fire diamond) | |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Nitrosylruthenium(II) nitrate refers to a group of mostly ill-defined inorganic metal nitrosyl complexes with the general formula Ru(NO)Lx(NO3)y, where L is a ligand. They are all orange or red amorphous and glassy solids. The only well-characterized simple nitrosylruthenium(II) trinitrate is the diammine complex, RuNO(NH3)2(NO3)3, which is a yellow crystalline solid.
History
[edit]The first nitrosylruthenium compound to be prepared was the 'chloride' (formulated Ru(NO)Cl3), first prepared by Karl Ernst Claus in 1844 while isolating and purifying ruthenium, but was wrongly identified as the chloro-ruthenate (K2RuCl6) by Jöns Jacob Berzelius due to the similar molecular weight of chloride (MW = 35.45) and nitrosyl (MW = 30.00). It was later correctly characterized by Antoine Joly in 1888, who also produced the 'hydroxide', which he formulated as (RuNO)2O3·2H2O.[4][5]
Nitrate derivatives, however, were not identified until 1955. They were all produced by dissolving the 'hydroxide' in nitric acid, then evaporating the solution. Various ill-defined hydrates and basic solids have been reported.[1]
Structure
[edit]The solid commercially available as nitrosylruthenium(II) nitrate, nominally Ru(NO)(NO3)3, is a red-colored ill-defined mixture with the approximate formula Ru(NO)(NO3)2.13(OH)0.87(H2O)2.[3] Other simple nitrosylruthenium(II) nitrates are also not structurally characterized. This is likely due to the polymerization of nitratoaqua complexes via the OH and NO3 bridging groups.[6]
The only structurally characterized simple nitrosylruthenium(II) trinitrate through single-crystal X-ray diffraction is the diammine complex, RuNO(NH3)2(NO3)3. It consists of repeating distorted mer-[Ru(NO)(NH3)2(NO3)3] octahedra and crystallises in an orthorhombic crystal structure. However, the ruthenium centers are in two slightly different environments due to the different torsion angles between the two trans-coordinated nitrate anions. In the complex, the nitrosyl is N-bonded with a ~180° Ru-N-O bond angle signalling the presence of the NO+ cation.[6]
The fac isomer of the diammine complex has also been reported, but the structure has not been fully elucidated.[7]
Preparation and properties
[edit]The simple 'nitrosylruthenium(II) nitrate' is prepared by the reaction of ruthenium(III) chloride and nitrous acid, followed by the precipitation of the 'hydroxide', formulated "Ru(NO)(OH)3". The 'hydroxide' is then treated with nitric acid to yield the 'hydrated nitrosylruthenium(II) nitrate'. Heating to hydrate to 100 °C produces the 'anhydrous Ru(NO)(NO3)3'.[1]
It is soluble in various organic solvents, such as diethyl ether and methyl ethyl ketone. This property has been investigated for the solvent extraction of radioactive ruthenium from nitric acid solutions. It is also soluble in water, but slowly undergoes hydrolysis.[1][8]
'Nitrosylruthenium(II) nitrate' decomposes to ruthenium(IV) oxide at around 250 °C. It also reacts with various acids, such as oxalic acid, sulfuric acid, and hydrofluoric acid to produce other ill-defined nitrosylruthenium salts.[1]
Silicon dioxide-deposited 'nitrosylruthenium(II) nitrate' forms triruthenium dodecacarbonyl when heated under carbon monoxide.[9]
The preparation of the well-defined RuNO(NH3)2(NO3)3 is more complicated. First, ammonium pentachloronitrosoruthenate (produced from the reaction of ruthenium(III) chloride, sodium nitrite, and nitric acid in hydrochloric acid) is heated to 330 °C:[10][11]
- (NH4)2[Ru(NO)Cl5] → [Ru(NO)(NH3)2Cl3] + 2HCl↑
Then the resulting complex is reacted with an aqueous sodium nitrite solution:[12]
- 2 Ru(NO)(NH3)2Cl3 + 7 NaNO2 + H2O → 2 RuNO(NH3)2(NO2)2OH + 6NaCl + NaNO3 + 2NO↑
Finally, RuNO(NH3)2(NO2)2OH is reacted with concentrated nitric acid to yield diamminenitrosylruthenium(II) nitrate as the mer isomer. It is a yellow crystalline solid poorly soluble in water, ethanol, and acetone.[13][6]
Other complexes
[edit]| Name | Formula | Molar mass (g/mol) | Crystal system |
Space group |
Unit cell (Å) | Cell volume (Å3) | Density (g/cm3) | Note | Reference |
|---|---|---|---|---|---|---|---|---|---|
| Diamminenitrosylruthenium(II) nitrate | mer-[Ru(NO)(NH3)2(NO3)3] | 351.15 | Orthorhombic | P212121 | a = 7.64 b = 10.84 c = 24.03 Z = 8 |
1991 | 2.338 | yellow solid | [6] |
| Tetraamminenitratonitrosylruthenium nitrate | trans-[RuNO(NH3)4(NO3)](NO3)2 | 385.21 | Tetragonal | I4 | a = 7.82, c = 9.78 | 598 | 2.139 | yellow-orange solid | [7] |
| Monoclinic | Cm | a = 11.56, b = 7.99, c = 7.79, β = 127.1° | 574 | 2.230 | [13] | ||||
| Aquatetraamminenitrosylruthenium nitrate | trans-[RuNO(NH3)4(H2O)](NO3)3 | 403.23 | Tetragonal | I41/a | a = 18.28, c = 15.13 | 5055 | 2.119 | [13] | |
| [RuNO(NH3)2(H2O)(NO3)2]NO3·H2O | 387.18 | Monoclinic | P21 | a = 6.63, b = 13.44, c = 7.02, β = 114.3° | 570 | 2.256 | [12] | ||
| cis-[RuNO(NH3)2Py2(NO3)](NO3)2·H2O | 527.39 | Triclinic | P1 | a = 9.70, b = 9.81, c = 10.67, α = 97.4°, β = 102.7°, γ = 95.57° | 1.797 | [14] | |||
| RuNO(Py)2(NO3)3 | 475.31 | Monoclinic | P21/c | a = 8.92, b = 12.28, c = 15.91, β = 94.4° | 1737 | 1.638 | [15] | ||
References
[edit]- 1 2 3 4 5 6 Fletcher, J.M.; Jenkins, I.L.; Lever, F.M.; Martin, F.S.; Powell, A.R.; Todd, R. (1955). "Nitrato and nitro complexes of nitrosylruthenium". Journal of Inorganic and Nuclear Chemistry. 1 (6): 378–401. doi:10.1016/0022-1902(55)80048-6.
- ↑ PubChem. "Ruthenium, tris(nitrato-kappaO)nitrosyl-". pubchem.ncbi.nlm.nih.gov. Retrieved 2026-07-15.
- 1 2 "Ruthenium(III) nitrosylnitrate, Ru 31.3% min 1 g". Fisher Scientific. Retrieved 2026-07-15.
- ↑ Joly A. Compt. rend., 108, 854
- ↑ Joly A. Compt. rend., 107, 994
- 1 2 3 4 Vorobyev, V. A.; Emelyanov, V. A.; Baidina, I. A.; Piryazev, D. A. (2017). "First example of crystal structure of the nitrosoruthenium(II) trinitrato complex". Journal of Structural Chemistry. 58 (5): 975–982. doi:10.1134/S0022476617050171. ISSN 0022-4766.
- 1 2 Kabin, E. V.; Emel’yanov, V. A.; Vorob’yev, V. A.; Alferova, N. I.; Tkachev, S. V.; Baidina, I. A. (2012). "Reaction of trans-[RuNO(NH3)4(OH)]Cl2 with nitric acid and synthesis of ammine(nitrato)nitrosoruthenium complexes". Russian Journal of Inorganic Chemistry. 57 (8): 1146–1153. doi:10.1134/S0036023612050105. ISSN 0036-0236.
- ↑ Swain, Pravati; Mallika, C.; Srinivasan, R.; Mudali, U. Kamachi; Natarajan, R. (2013). "Separation and recovery of ruthenium: a review". Journal of Radioanalytical and Nuclear Chemistry. 298 (2): 781–796. doi:10.1007/s10967-013-2536-5. ISSN 0236-5731. Retrieved 2026-07-15.
- ↑ Huang, Lin; Xu, Yide (2001). "Surface-mediated reductive carbonylation of SiO2-supported RuCl3 and Ru(NO)(NO3)3 studied by IR spectroscopy". Journal of Molecular Catalysis A: Chemical. 176 (1–2): 267–280. doi:10.1016/S1381-1169(01)00267-9.
- ↑ V. A. Emel'yanov; S. P. Khranenko; A. V. Belyaev (2001). "Nitrosation of Ruthenium Chloro Complexes". Russian Journal of Inorganic Chemistry. 46 (3): 346–351.
- ↑ Il’in, M. A.; Emel’yanov, V. A.; Baidina, I. A. (2008). "Structure and synthesis of nitrosoruthenium trans-diammines [Ru(NO)(NH3)2Cl3] and [Ru(NO)(NH3)2(H2O)Cl2]Cl·H2O". Journal of Structural Chemistry. 49 (6): 1090–1097. doi:10.1007/s10947-008-0183-4. ISSN 0022-4766.
- 1 2 Il’in, M. A.; Kabin, E. V.; Emel’yanov, V. A.; Baidina, I. A.; Vorob’yov, V. A. (2009). "trans-dinitro- and trans-dinitratoruthenium complexes [RuNO(NH3)2(NO2)2(OH)] and [RuNO(NH3)2(H2O)(NO3)2]NO3·H2O". Journal of Structural Chemistry. 50 (2): 328–334. doi:10.1007/s10947-009-0045-8. ISSN 0022-4766.
- 1 2 3 Kabin, E. V.; Emel’yanov, V. A.; Baidina, I. A.; Nedoseykina, T. I.; Vorob’yov, V. A. (2010). "XRD and EXAFS study of nitrato ammine complexes of nitrosyl ruthenium". Journal of Structural Chemistry. 51 (S1): 73–80. doi:10.1007/s10947-010-0192-y. ISSN 0022-4766.
- ↑ Vorobyev, Vasily; Kostin, Gennadiy A.; Baidina, Iraida A.; Mikhailov, Artem A.; Korolkov, Ilya V.; Emelyanov, Vyacheslav A. (2020-01-31). "Synthesis of the Ruthenium Nitrosyl Complex with Coordinated Ammonia and Pyridine at Room Temperature". Zeitschrift für anorganische und allgemeine Chemie. 646 (2): 58–64. doi:10.1002/zaac.201900246. ISSN 0044-2313.
- ↑ Kostin, G. A.; Nikiforov, Ya. A.; Kuratieva, N. V. (2020). "Synthesis and Structure of Ruthenium Nitroso Complexes with Nitrate Anions and Pyridine as Ligands". Journal of Structural Chemistry. 61 (1): 86–94. doi:10.1134/S0022476620010096. ISSN 0022-4766.