DOI: I0.i7344/acsi.20i6.2373_Acta Chim. Slov. 2016, 63, 369-375_ 359
Scientific paper
Oxidation of Ruthenium and Iridium Metal by XeF2 and Crystal Structure Determination of [Xe2F3][RuF6]-XeF2 and [Xe2F3][MF6] (M = Ru, Ir)
Melita Tramšek*, Evgeny Goreshnik and Gašper Tavčar
Jožef Stefan Institute, Jamova 39, SI-1000 Ljubljana, Slovenia * Corresponding author: E-mail: melita.tramsek@ijs.si
Received: 23-03-2016
Abstract
Salts containing [Xe2F3]+ cations and [MF6]- anions (M = Ru, Ir) were synthesized by the oxidation of metal with excess of XeF2 in anhydrous hydrogen fluoride (aHF) as a solvent. Single crystals of [Xe2F3][RuF6]-XeF2, [Xe2F3][RuF6] and [Xe2F3][IrF6] were grown by slow evaporation of the solvent. [Xe2F3][RuF6]-XeF2 crystallizes in a triclinic P-1 space group (a = 8.3362(1) À, b = 8.8197(2) À, c = 9.3026(4) À; a= 68.27(1)°, /J = 63.45(1)°, y= 82.02°, V = 568.09(9) À3 (Z = 2)). Discrete [Xe2F3]+, XeF2 and [RuF6]- units are found in the asymmetric unit. [Xe^][RuF6] and [Xe2F3][IrF6] compounds are isostructural and crystallize in a monoclinic Cc space group (a = 14.481(3) À (Ru); 14.544(3) À (Ir); b = 8.0837(8) À (Ru), 8.0808(7) À (Ir), c = 10.952(2) À (Ru), 11.014(2) À (Ir); P = 136.825(6)° (Ru), 139.954(7)°, V = 877.2(3) À3 (Ru), 883.6(3) À3 (Ir); Z = 4). The asymmetric unit in the [Xe2F3][MF6] (M = Ru, Ir) consists of one [Xe2F3]+ and one [MF6]- unit.
Keywords: Noble gas fluorides, ruthenium, iridium, crystal structure
1. Introduction
acterized. The compounds with composition 1:1
XeF2 is the most stable and easily handled noble gas (XeF+MF6) and 1:2 (XeF+M2F11 ) were obtained for the
fluoride and therefore its chemistry is very extensive. Basic information about XeF2, its properties and the possibilities that it offers can be found in review paper and book and the references listed therein.12 One of its unexpected and interesting abilities is also binding to metal centres in order to form coordination compounds. A large variety of such compounds has been found in previous years.3 The formation of XeF2 adducts with main-group and transition-metal Lewis acidic pentafluoridometalates - MF5 is known for decades. So far three types of such compounds were found: 2XeF2 MF5, XeF2 MF5 and XeF2 (MF5)2. The degree of ionic character in these compounds varies depending on the Lewis acidity of the respective pentafluoride. Compounds were mainly characterized by vibrational spectroscopy and can be written as salts [Xe2F3][MF6], [XeF][MF6] and [XeF][M2F11], especially in the case of reactions with strong Lewis acids (for example AsF5, SbF5, BiF5 ...). The formation of 2:1 compounds was found in the cases where M was As, Sb, Bi, Ta, Ru, Os and Ir.4,5,6,7 From this type of compounds (2:1 composition) [Xe2F3][MF6] (M = As, Sb)8,9 were also structurally char-
most of the MF5 mentioned above. Some of them were structurally characterized: [XeF][MF6] (M = As, Sb, Bi, Ru and Ir)10111213 and [XeF][M2F11] (M = Sb, Bi).11 One of the latest structurally characterized examples is also and [XeF][IrSbF11] with two different metals in the anion.13 [Xe2F3]+ and [XeF]+ cations were recently found with nonoctahedral anion in the xenon(II) polyfluoridoti-tanates(IV): [Xe2F3][Ti8F33] and [XeF]2[Ti9F38].14
The present study reports about the synthesis and structural characterization of three noble gas salts containing [Xe2F3]+ cation: [Xe2F3][RuF6]XeF2, [Xe2F3][RuF6] and [Xe2F3][IrF6].
2. Experimental
2. 1. General Experimental Procedure and Reagents
Volatile materials (anhydrous HF, F2) were handled in an all PTFE vacuum line equipped with PTFE (polyte-
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trafluoroethylene) valves. The manipulations of the nonvolatile materials were carried out in a glove-box (M. Braun). The residual water in the atmosphere within the glove-box never exceeded 1 ppm. The reactions were carried out in FEP (tetrafluoroethylene-hexafluoropropylene; Polytetra GmbH, Germany) reaction vessels (height 250-300 mm with inner diameter 16 mm and outer diameter 19 mm) equipped with PTFE valves and PTFE coated stirring bars. T-shaped reaction vessels from PTFE, which were constructed as described earlier, were used for the crystallization process.15 Prior to their use all reaction vessels were passivated with elemental fluorine. Fluorine was used as supplied (Solvay Fluor and Derivate GmbH, Germany). Anhydrous HF (Linde, 99.995%) was treated with K2NiF6 (Advance Research Chemicals, Inc.) for several hours prior to use. XeF2 was synthesized by photochemical reaction between Xe and F2.16 Caution: aHF, F2 and XeF2 must be handled with great care in a well-ventilated fume hood, and protective gear must be worn at all times.
2. 2. Synthesis and Characterization Procedures
Synthetic procedures for the ruthenium and iridium compounds were the same. Metal powder (Ru: 0.215 g, 2.13 mmol, Ir: 0.430 g, 2.20 mmol) was added into a reaction vessel inside the glove-box. The aHF was condensed into the reaction vessel at -196 °C at the vacuum line. Large excess of XeF2 (mole ratio M : XeF2 was approximately 1:10) was weighed into another reaction vessel inside the glove-box. Anhydrous HF was added to the XeF2 and the reaction vessel was warmed up to room temperature. These two reaction vessels (one with the suspension of the metal, and another with dissolved XeF2) were attached in a T-shape manner and additional valve was used in order to provide completely closed system. The XeF2 solution was then poured into cold reaction vessel (-196 °C) with suspension of the metal powder (Ru, Ir). The reaction vessel was left to slowly warm up to room temperature. The solution turned immediately green in the case of ruthenium but the reaction with iridium proceeded at room temperature for several days (light gray solid product). Products of the oxidation were isolated by removal of aHF and excessive XeF2 under dynamic vacuum at room temperature. Several crystallization experiments were performed. In some cases the product of the oxidation of the metal with XeF2 was dissolved in aHF in a wider arm of the T-shaped crystallization vessel, while in the other additional XeF2 was added. Solution was then poured into narrow arm of the crystallization vessel and left to crystallize by a small temperature gradient used for slow evaporation of aHF.
The Raman spectra were recorded at room temperature with a Horiba Jobin Yvon LabRam-HR spectrometer equipped with an Olympus BXFM-ILHS microscope and
CCD detector. The samples were excited by the 632.8 nm emission line of a He-Ne laser. Samples for measurement were transferred into the quartz capillary inside glove-box.
The crystallographic parameters and summaries of data collection for all compounds are presented in Table 1. Single-crystal data were collected on a Rigaku AFC7 dif-fractometer using graphite monochromatized MoKa radiation at 200 K. Crystals were immersed into perfuorinated oil in glove-box and further on selected under the microscope. An empirical multi-scan absorption correction was applied. All structures were solved by direct methods using SIR-9217 and SHELXS-97 programs (teXan crystallo-graphic software package of Molecular Structure Corporation)18 and refined with SHELXL-97 software,19 implemented in program package WinGX.20 Full-matrix least-squares refinements based on F2 were carried out for the positional and thermal parameters for all non-hydrogen atoms. The figures were prepared using DIAMOND 3.1 software.21 Further details of the crystal-structure investigation may be obtained from the Fachinformationszentrum Karlsruhe, 76344 Eggenstein-Leopoldshafen, Germany, on quoting the depository number: CSD-430805 for [Xe2F3][RuF6], CSD-430806 for [Xe2F3][IrF6] and CSD-430807 for [Xe2F3][RuF6]XeF2, respectively.
3. Results and Discussion
The oxidation power of XeF2 was used in order to prepare previously mentioned Ru(V) and Ir(V) compounds. XeF2 dissolved in anhydrous hydrogen fluoride (aHF) was also used as selective inorganic fluorinating reagent for oxidation and fluorination of Ir and RuF3 almost three decades ago with final products being IrF5 and RuF5.22 Ruthenium metal was oxidized rapidly with vigorous reaction being observed during the warming of the reaction vessel from -196 °C to room temperature. A clear, slightly green solution was obtained. We used a slightly modified procedure for the preparation of the ruthenium compound ([Xe2F3][MF6]XeF2). The product was further used for the synthesis of [Ba(XeF2)5][RuF6]2.23 The same reaction with iridium proceeded for several weeks. The colour of the solution was red-brown at the beginning and after several days became slightly yellow with some grey precipitate -same as the solid product after its isolation. The grey solid obtained by the oxidation of Ir metal with XeF2 was re-dissolved in aHF and a clear, slightly green solution was obtained. Products of the reactions were also monitored by Raman spectroscopy, which shows (Figure 1) that in both cases the compound with composition [Xe2F3][MF6] nXeF2 (M = Ru, Ir, n is approx. 1 according to the mass balance of the reaction) were obtained. An alternative method used for the preparation of related compounds with Ru(V) (KRuF6, LiRuF6 ) and Ir(V) (KIrF6, LiIrF6) with al-
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kaline metals is the room temperature oxidation with elemental fluorine in the presence of Lewis base (KF) in aHF.24,25 One of the recently published ways to prepare soluble iridium compounds, which seems to be important for modern "urban mining", is the reaction of the metal with tetrafluorobromates (MBrF4; M = K, Rb, Cs).26
a)
b)
Figure 1. Raman spectra of [Xe2F3][RuF6]-XeF2 (a) and ^FJPrFJ^ (b)
For solid XeF2 the band at 497 cm-1 is characteristic.27 The bands at 506 cm-1, 515 cm-1 in ruthenium compound and 506 cm-1 and 516 cm-1 in iridium compound can be attributed to the XeF2 weakly associated with
[Xe2F3]+ cations and [MF6]- anions in the [Xe2F3] [MF6] XeF2 product. Similar positions and assignment of these bands were observed in some other cases in the system XeF2-MF5 (M = Sb, Ta, Nb). The weakly associated XeF2 was found in the melt of the compounds.28 "Free" XeF2 was also found in the compounds XeF2XeF6AsF5 and XeF22(XeF6)2(AsF5), where the Raman bands depend on the interaction of the so called "free" XeF2 molecule with cations and anions and consequential distortion of its shape. "Free" XeF2 in XeF2-2(XeF6)-2(AsF5) is probably in a completely symmetric environment, therefore the band assigned to it coincides with the symmetric stretching frequency in molecular XeF2 (497 cm-1). On the other hand Raman spectrum of XeF2XeF6AsF5 doesn't show a symmetric vibration of molecular XeF2 but two bands at 557 cm-1 and 429 cm-1 which represent a distorted XeF2 molecule meaning that XeF2 in this compound can be far from "free".29 Linear distortion of XeF2 was found also in the Raman spectrum of XeF2 • [XeF5] [RuF6].30 Bands at 578 cm-1 and 586 cm-1 in the ruthenium compound and bands at 578 cm-1 and 587 cm-1 in iridium compound can be confidently assigned to the Xe-Ft stretch vibrations of the [Xe2F3]+ cation. They are in the region that is characteristic for such vibrations (from ca. 575 cm-1 to 600 cm-1). The bands at 646 cm-1, 667 cm-1 and 265 cm-1 for the ruthenium compound and 662 cm-1 and 243 cm-1 for the iridium can be assigned to the vibration of the [MF6]- anions. Products with additional XeR are not stable under
Figure 2: Raman spectra of the reaction mixture during the isolation of ruthenium compound on the vacuum system: a.) mixture of [Xe2F3][RuF6] •XeFj, [Xe2F3][RuF6] and [XeF][RuF6]; b.) mixture of [Xe2F3][RuF6] and [XeF] [RuF6]; c.) [XeF][RuF6].
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dynamic vacuum at room temperature. They release XeF2, which leads to the formation of the [Xe2F3][MF6] and further on to the [XeF][MF6] (M = Ru, Ir) compounds. According to the mass balance of the reactions and Raman spectra, the [XeF][MF6] (M = Ru, Ir) salts seem to be stable at room temperature under dynamic vacuum. Raman analysis of the slow removal of XeF2 under dynamic vacuum in the case of ruthenium is shown in Figure 2. In the spectrum shown on the Figure 2a (black colour) all three phases can be found: [Xe2F3][RuF6]XeF2, [Xe2F3][RuF6] and [XeF][RuF6]. With the release of the XeF2, phases [Xe2F3][RuF6] and [XeF][RuF6] are found (Figure 2b (blue colour)). Prolonged pumping on the vacuum system (overnight) ended up with [XeF][RuF6] as the only product. Position and the intensities of the bands for [Xe2F3][RuF6] and [XeF][RuF6] are in the agreement with those published previously.4
3. 1. Crystal Structure Determination of [Xe2F3][RuF6]-XeF2 and [Xe2F3][MF6] (M = Ru, Ir)
Three compounds in this system were structurally characterized. Summary of crystal data and refinement re-
sults for [Xe2F3][RuF6] XeF2 and [Xe2F3][MF6] (M = Ru, Ir) are presented in Table 1 and selected distances and angles are found in Table 2. Several unsuccessful attempts were made in order to prepare suitable single crystals of the [Xe2F3][IrF6]XeF2. So far we were only able to resolve the structure of [Xe2F3][IrF6].
The structure of [Xe2F3][RuF6] XeF2 consists of discrete [Xe2F3]+, XeF2 and [RuF6]- units (Figure 3). XeF2 molecules and [Xe2F3]+ cations are oriented roughly perpendicularly to each other. When viewed along (-3 -4 3) direction alternating cationic and anionic layers could be seen. Anions are separated by XeF2 molecules (Figure 4). The compound is structurally related to [Kr2F3][SbF6]KrF2 in which the crystal packing consists of alternating cation and equally populated anion/KrF2
layers.31
XeF2 molecules are nearly linear with distances being 1.980(7) and 1.992(7) A and angle F10-Xe-F11 of 178.9(4)°. [Xe2F3]+ cation exhibit a planar, V shape configuration with nearly symmetrical Xe-Ft bonds (2.139(7) and 2.152(7) A) and a Xe-Fb-Xe angle of 154.3(4)°. The [RuF6]- anions are slightly distorted octa-hedra with Ru-F bond distances in the range from 1.834(8) to 1.861(7) A.
Table 1. Crystal data and structure refinement for [Xe2F3][RuF6]-XeF2 and Xe2F3MF6 (M = Ru, Ir)
	[Xe2F3][RuF6]XeF2	[Xe2Fj[RuF6]	[Xe2F3][IrF6]
Empirical formula	RuXe3Fjj	RuXe2F9	IrXe2F9
Formula weight	703.94	534.67	625.8
Wavelength, MoKa	0.71069 À	0.71069 À	0.71069 À
Crystal system,			
Space group	triclinic	monoclinic	monoclinic
	P-1	Cc	Cc
Temperature, K	200	200	200
Unit cell dimensions			
a, Ä	8.3362(1)	14.481(3)	14.544(3)
b, Ä	8.8197(2)	8.0837(8)	8.0808(7)
c, Ä	9.3026(4)	10.952(2)	11.014(2)
a, °	68.27(1)	90	90
ß,°	63.45(1)	136.825(6)	136.954(7)
Y, °	82.02(2)	90	90
V, Ä3	568.09(9)	877.2(3)	883.6(3)
Z	2	4	4
Calculated density, g/cm3	4.115	4.048	4.704
Absorption coeff., mm-1	10.289	9.477	22.745
F(000)	610	932	1064
Crystal size, mm	0.08x0.06x0.04	0.10x0.10x0.08	0.10x0.07x0.05
Colour	colourless	colourless	colourless
Theta range for data collection, deg	2.487-28.6986	3.2522-28.5637	3.1256-27.9323
Limiting indices	-8 < h < 11, -10 < k	-18 < h < 16, -10 < k	-18 < h < 17, -6
	< 11, -11 < l < 12	< 10, -8 < l < 14	< k < 10, -6 < l < 14
Measured reflections	2259	1174	1129
Used in refinement	1837	890	1074
Free parameters	137	111	111
Goodness-of-fit on F2	1.134	1.134	1.067
R indices	R1 = 0.0608	R1 = 0.0371	R1 = 0.0382
	wR1 = 0.1775	wR1 = 0.0849	wR1 = 0.0963
Largest diff. peak and hole, e Ä-3	1.758 and -3.063	1.579 and -1.236	1.699 and -2.329
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Table 2. Selected distances (Â) and angles (°) in [Xe2F3][RuF6] XeF2, [Xe2F3][MF6] (M = Ru, Ir)
	[Xe2F3][RuF6]	[Xe2Fj]	^FJ
	• XeF2	[RuF6]	[IrF6]
Xe1-F1	2.139(7)	2.09(1)	2.12(2)
Xe2-F1	2.152(7)	2.17(1)	2.15(2)
Xe1-F2	1.913(8)	1.90(2)	1.88(2)
Xe2-F3	1.919(6)	1.92(2)	1.96(2)
Xe3-F10	1.980(7)		
Xe3-F11	1.992(7)		
Xe1-F1-Xe2	154.3(4)	161.5(5)	161.3(8)
F10-Xe3-F11	178.9(4)		
Figure 3. Asymmetric unit in [Xe2F3][RuF6]-XeF2 with thermal ellipsoids drawn at 50 % probability level.
The Xe centres from both XeF2 and [Xe2F3]+ moieties interact with fluorine atoms from another structural units. The shortest F9 - Xe2in and F9 - Xe1 distances of 3.190(7) and 3.216(7) A respectively correspond to slightly elongated Ru1-F9 bond (1.861(7) A). There are four XeF2 molecules bound to one anion via Xe-F contacts of 3.301(7)-3.373(7) A. Terminal F2 and F3 atoms from each [Xe2F3]+ also form longer contacts with Xe centres from other cations. These contacts are slightly longer (from 3.219(7) to 3.278(8) A, correspondingly) than those in the case of XeF2 molecules.
Weak Xe-F(Xe) and Xe-F(Ru) interactions connect above mentioned units into three-dimensional network (Figure 4) if contacts shorter than 3.4 A are taken into consideration. The sum of the van der Waals radius for xenon (2.16 A) and fluorine (1.35 A) is 3.51 A.32
eral Xe-F contacts in the range above 3 A can be found. A packing diagram along the b-axis is presented in Figure 6. A less bent structure of the [Xe2F3]+ cation is found in the case of [Xe2F3][MF6] (M = Ru, Ir) compared to the [Xe2F3][RuF6]XeF2. The Xe-Fb-Xe angle is 161.5(5)° in the ruthenium compound and 161.3(8)° in the iridium compound. These angles are in agreement with those in isostructural monoclinic [Xe2F3][SbF6] (Xe -Fb -Xe = 160.3 °). Bridging angle of Xe-Fb-Xe in [Xe2F3]+ cations vary from 139.8° as observed in trigonal [Xe2F3] [AsF6]9 to the widest one being 164.3° as observed in [Xe^irT^J.14
Strong dependence of the Xe-Fb-Xe bridge angle on the crystal packing and on the nature of the counter anion was demonstrated in a previous study. Calculation (Christiansen-Ermler ECP) in the same study also predicted non-linear structure of the [Xe2F3]+ cation with a bridging angle of 168°.9
Figure 5. Asymmetric units in [Xe2F3][RuF6] and [Xe2F3][IrF6] with thermal ellipsoids drawn at 50 % probability level.
Figure 6. Packing diagram of [Xe2F3][RuF6] along b-axis.
Figure 4. Packing diagram of [Xe2F3][RuF6]-XeF2.
The [Xe2F3][MF6] (M = Ru, Ir) salts are both isostructural with monoclinic [Xe2F3][SbF6].9 Asymmetrical unit in both cases consists of one [Xe2F3]+ cation and one [MF6]- anion (Figure 5). In both cases sev-
4. Conclusions
The oxidizing power of XeF2 was demonstrated by oxidation of ruthenium and iridium metal in aHF as a solvent. Products of the oxidation belong to the family of no-
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ble gas compounds with [Xe2F3]+ cations. Salt with composition [Xe2F3][RuF6] ■ XeF2 was structurally characterized. The synthesis and characterization with Raman spectroscopy of the new salt [Xe2F3][IrF6]XeF2 are also reported. Single crystal structures of [Xe2F3][RuF6] and [Xe2F3][IrF6] were determined.
5. Acknowledgement
The authors gratefully acknowledge the Slovenian Research Agency (ARRS) for financial support of the Research Program P1-0045 (Inorganic Chemistry and Technology).
6. References
1.	M. Tramsek, B. Zemva, Acta Chim. Slov. 2006, 53, 105-116.
2.	J. Reedjik, K. Poeppelmeier (Ed.): Comperhensive Inorganic Chemistry II, Elsevier, Oxford, 2013, D. S. Brock, G. J. Schrobilgen, B. Zemva, Vol. 1, pp755-822
3.	M. Tramsek, G. Tavcar, J. Fluorine Chem. 2015, 174, 14-21. http://dx.doi.org/10.10167j.jfluchem.2014.08.009
4.	F. O. Sladky, P. A. Bulliner, N. Bartlett, J. Chem. Soc. 1969, 2179-2188. http://dx.doi.org/10.1039/J19690002179
5.	B. Frlec, J. H. Holloway, J. Chem. Soc. 1975, 535-540.
6.	J. Gillespie, D. Martin, G. J. Schrobilgen, J. Chem. Soc. Dalton 1980, 1898-1903.
7.	J. H. Holloway, J. G, Knowles, J. Chem. Soc. 1969, 756-761. http://dx.doi.org/10.1039/j19690000756
8.	N. Bartlett, B. G. DeBoer, F. J. Hollander, F. O. Sladky, D. H. Templeton, A. Zalkin, Inorg. Chem. 1974, 13, 780-785. http://dx.doi.org/10.1021/ic50134a004
9.	B. A. Fir, M. Gerken, B. E. Pointner, H. P. A. Mercier, D. A. Dixon, G. J. Schrobilgen, J. Fluorine Chem. 2000, 105, 159-167.
http://dx.doi.org/10.1016/S0022-1139(00)00306-7
10.	A. Zalkin, D. L. Ward, R. N. Biagoni, D. H. Tempelton, N. Bartlett, Inorg. Chem. 1978, 17, 1318-1322. http://dx.doi.org/10.1021/ic50183a044
11.	H. St. A. Elliot, J. F. Lehman, H. P. A. Mercier, H. D. B. Jenkins, G. J. Schrobilgen, Inorg. Chem. 2010, 49, 8504-8523.
12.	N. Bartlett, M. Gennis, D. D. Gibler, B. K. Morrell, A. Zalkin, Inorg. Chem. 1973, 12, 1717-1721. http://dx.doi.org/10.1021/ic50126a002
13.	F. Tamadon, S. Seidel, K. Seppelt, Acta Chim. Slov. 2013, 60, 491-494.
14.	K. Radan, E. Goreshnik, B. Zemva, Agew. Chem. Int. Ed. 2014, 53, 13715-13719.
15.	M. Lozinsek, E. Goreshnik, B. Zemva, Acta Chim. Slov. 2014, 61, 542-547.
16.	R. N. Grimes (Ed.). Inorganic Syntheses, John Wiley, New York, 1992, A. Šmalc, K. Lutar, Vol. 29, pp. 1-4.
17.	A. Altomare, M. Cascarano, M., C. Giacovazzo, A. Guagliardi, J. Appl. Cryst. 1993, 26, 343-350. http://dx.doi.org/10.1107/S0021889892010331
18.	Molecular Structure Corporation. (1997-1999), teXsan for Windows, Single Crystal Structure Analysis Software. Version 1.06, MSC, 9009 New Trails Drive, The Woodlands, TX 77381, USA.
19.	G. M. Sheldrick, Acta Cryst. 2008, A64, 112-122. http://dx.doi.org/10.1107/S0108767307043930
20.	L. J. Farrugia, J. Appl. Cryst. 1999, 32, 837-838. http://dx.doi.org/10.1107/S0021889899006020
21.	DIAMOND v3.1, Crystal Impact GbR, Bonn, Germany, 2004-2005
22.	R. C. Burns, I. D. MacLeod, T. A. O'Donnell, T. E. Peel, K. A. Philips, A. B. Waugh, J. Inorg. Nucl. Chem. 1977, 39, 1737-1739.
http://dx.doi.org/10.1016/0022-1902(77)80193-0
23.	T. Bunic, M. Tramsek, E. Goreshnik, B. Zemva, Collect. Czech. Chem. Commun. 2008, 73, 1645-1654. http://dx.doi.org/10.1135/cccc20081645
24.	G. Lucier, S. H. Elder, L. Chacon, N Bartlett, Eur. J. Solid State Inorg. Chem. 1996, 33, 809-820.
25.	G. Tavcar, B. Zemva, Inorg. Chem. 2013, 52, 4139-4323. http://dx.doi.org/10.1021/ic302323j
26.	S. Ivlev, P. Woidy, F. Kraus, I. Gerin, R. Ostvald, Eur. J. Inorg. Chem. 2013, 4984-4987.
http://onlinelibrary.wiley.com/doi/10.1002/ejic.201300618/ abstract
27.	P. A. Agron, G. M. Begun, H. A. Levy, A. A. Mason, C. G. Jones, D. F. Smith, Science 1963, 139, 842-844. http://dx.doi.org/10.1126/science.139.3557.842
28.	B. Frlec, J. H. Holloway, J. Inorg. Nucl. Chem. Supplement 1 1976, 28, 167-171.
29.	N. Bartlett, M. Wechsberg, Z. anorg. Allg. Chem. 1971, 385, 5-17. http://dx.doi.org/10.1002/zaac.19713850103
30.	B. Zemva, L. Golic, J. Slivnik, Vestn. Slov. Kem. Druš. 1983, 30, 365-376.
31.	J. F. Lehman, D. A. Dixon, G. J. Schrobilgen, Inorg. Chem. 2001, 40, 3002-3017. http://dx.doi.org/10.1021/ic001167w
32.	A. Bondi, J. Phys. Chem. 1964, 68, 441-451. http://dx.doi.org/10.1021/j100785a001
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Povzetek
Z oksidacijo kovine (Ru, Ir) s presežnim XeF2 v brezvodnem vodikovem fluoridu (aHF) kot topilu smo pripravili spojine s kationi [Xe2F3]+ in anioni [MF6]- (M = Ru, Ir). Kristale [Xe2F3][RuF6] • XeF2, [Xe2F3][RuF6] in [Xe2F3][IrF6], ki so bili primerni za rentgensko strukturno analizo, smo pripravili s počasnim izhlapevanjem topila. [Xe2F3][RuF6] • XeF2 kristalizira v triklinskem kristalnem sistemu; prostorska skupina P-1 (a = 8,3362(1) A, b = 8,8197(2) A, c = 9,3026(4) A; a= 68,27(1)°, P= 63,45(1)°, Y = 82,02°, V = 568,09(9) A3 (Z = 2)). V asimetrični enoti spojine se nahajajo [Xe2F3]+, XeF2 in [RuF6]-. Spojini [Xe2F3][RuF6] in [Xe2F3][IrF6] sta izostrukturni in kristalizirata v monoklinskem kristalnem sistemu; prostorska skupina Cc (a = 14,481(3) A (Ru); 14,544(3) A (Ir); b = 8,0837(8) A (Ru), 8,0808(7) A (Ir), c = 10,952(2) A (Ru), 11,014(2) A (Ir); P = 136,825(6)° (Ru), 139,954(7)°, V = 877,2(3) A3 (Ru), 883,6(3) A3 (Ir); Z = 4). Asimetrični enota [Xe2F3][MF6] (M = Ru, Ir) je sestavljena iz [Xe2F3]+ in [MF6]- ionov.
Tramsek et al.: Oxidation of Ruthenium and Iridium Metal