Syntheses of [Rh(NH3)5Cl][MCl6] (M = Re, Os, Ir) and Investigation of Their Thermolysis Products. Crystal Structure of [Rh(NH3)5Cl][OsCl6]

Binary complex salts [Rh(NH₃)₅Cl][MCl₆], where M = Re, Os, Ir, have been synthesized and characterized. X-ray diffraction analysis indicated that the salts are isostructural. According to X-ray phase analysis, the products of their thermolysis in hydrogen are monophase stoichiometric nonequilibrium solid solutions Rh_0.5M_0.5 (M = Re, Os, Ir). The molecular and crystal structures of [Rh(NH₃)₅Cl][OsCl₆] were determined in an X-ray structural analysis.     

Double complex salts [M(NH3)5Cl][M′Br4] (M = Rh, Ir, Co, Cr, Ru; M′ = Pt, Pd): Synthesis, x-ray diffraction characterization, and thermal properties

Double complex salts (DCSs) with [M(NH₃)₅Cl]²⁺ (M = Rh, Ir, Co, Cr, Ru) cations and [PtBr₄]^2? anions were prepared in high yields. The salts were two-phase mixtures of the anhydrous and monohydro DCSs. Anhydrous analogues containing [PdBr₄]^2? anions with M = Cr or Ru were synthesized. All the compounds were characterized using a set of physicochemical methods. The crystal structure of chloropentaamminechromium(III) tetrabromopalladate(II) was solved: space group Pnma, Z = 4, a = 17.068(2) Å, b = 8.315(12) Å, c = 9.653(14) Å. The [M(NH₃)₅Cl][M′X₄] (M = Rh, Ir, Co, Cr, Ru; M′ = Pd, Pt; X = Cl, Br) compounds were shown to be isostructural. The [M(NH₃)₅Cl][PtBr₄] · H₂O monohydrates are isostructural to the [M(NH₃)₅Cl][PdCl₄] · H₂O monohydrates (space group P2₁/c, z = 4). The properties of the compounds were comparatively analyzed. The tendencies of the thermal stability of the complexes were elucidated. The thermolysis products of the double complex salts obtained under a helium or hydrogen atmosphere were studied.     

Crystal Structure of [M(NH3)5Cl]2[IrCl6]Cl2 (M = Co, Rh, Ir) Binary Complex Salts

Binary complex salts of M(NH₃)₅Cl]₂[IrCl₆]Cl₂ composition, where M = Co(III), Rh(III), or Ir(III), have been studied. All phases are isostructural with [M(NH₃)₅Cl]₂[PtCl₆]Cl₂ complexes [M = Rh(III) and Ir(III)]; Xray structural and crystallochemical analysis have been performed.     

Solid solutions Ru<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ir<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> synthesized by thermolysis of coordination compounds

The double complex salts [Ir(NH₃)₅Cl][IrCl₆], [Ru(NH₃)₅Cl][IrCl₆], and [Ru(NH₃)₅Cl]₂[IrCl₆]Cl₂ have been synthesized and characterized. An X-ray diffraction study demonstrated that these salts are isostructural with [Rh(NH₃)₅Cl][OsCl₆] and [Ir(NH₃)₅Cl]₂[PtCl₆]Cl₂ synthesized earlier. Thermolysis of these salts in hydrogen and helium has been studied. X-ray powder diffraction analysis show that thermolysis yields stoichiometric solid solutions of metals as the final products. The unit cell parameters of these products correspond to equilibrium phases.     

Synthesis, structure, and thermal transformations of double complex salts [Au(C4H13N3)Cl][MCl6]· nH2O (M = Ir, Pt; n = 0–2)

Double complex salts [Au(C₄H₁₃N₃)Cl][MCl₆]·nH₂O (M = Ir, Pt; n = 0–2) were synthesized. According to X-ray diffraction data, compounds with n = 1.5 are isostructural; the crystal structure is composed of the complex cations [Au(dien)Cl]²⁺ (dien is diethylenetriamine), the complex anions [MCl₆]²⁻, and water molecules of crystallization. Thermolysis of the double complex salts under hydrogen and helium was studied. The formation of nonequilibrium solid solutions based on Ir in the Au-Ir system and based on Pt in the Au-Pt system was demonstrated. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 416–421, March, 2006.     

Synthesis of [M(NH3)5Cl](ReO4)2 (M = Cr, Co, Ru, Rh, Ir) and investigation of thermolysis products. Crystal structure of [Rh(NH3)5Cl](ReO4)2

Complex salts [M(NH₃)₅Cl](ReO₄)₂, where M = Cr, Co, Ru, Rh, Ir, have been prepared. The crystal structure of [Rh(NH₃)₅Cl](ReO₄)₂ was determined by single crystal X-ray diffraction. Crystal data: a = 17.369(4) Å, b = 7.7990(16) Å, c = 11.218(2) Å, V = 1430.5(5) ų, space group C2/m, Z = 4, d _calc = 3.19 g/cm³, R = 0.0447. Complex salts from the above series are shown to be isostructural; they were defined by X-ray crystallography. Thermal decomposition of the compounds in an inert atmosphere and under hydrogen has been studied. According to X-ray phase analysis (XRPA) data, the M_0.33Re_0.67 (M = Co, Ru, Rh, Ir) monophase solid solutions are the products of reduction of the salts under hydrogen.     

X-ray diffraction study of [M<Superscript>I</Superscript>(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>Cl] [M<Superscript>II</Superscript>Br<Subscript>6</Subscript>] (M<Superscript>I</Superscript> = Rh,Ir; M<Superscript>II</Superscript> = Re,Ir) polycrystals

Based on the X-ray diffraction data for polycrystals, the crystal structures of double complex salts [Rh(NH₃)₅Cl][ReBr₆] and [Ir(NH₃)₅Cl][ReBr₆] are refined. The structure of [Rh(NH₃)₅Cl][IrBr₆] is determined. Initial models are constructed using the Monte Carlo method in the straight space. Further refinement is made by the Rietveld method. It is shown that such an approach is suitable for the refinement of crystal structures composed of isolated rigid polyhedra and can be used to determine the structure of salts without structural analogues     

Synthesis, properties, and thermal decomposition products of [Ru(NH3)5Cl][PtCl6] and [Ru(NH3)5Cl]2[PtCl6]Cl2

The double complex salts [Ru(NH₃)₅Cl][PtCl₆] (I) and [Ru(NH₃)₅Cl]₂[PtCl₆]Cl₂ (II) were synthesized and studied by X-ray diffraction. They were found to be isostructural to the previously synthesized [Rh(NH₃)₅Cl][OsCl₆] and [Ir(NH₃)₅Cl]₂[PtCl₆]Cl₂. The thermolysis of the complexes in the atmosphere of hydrogen and helium was studied by the powder X-ray diffraction analysis. The product of the salt I thermolysis is a single-phase solid solution Ru_0.5Pt_0.5 (a = 3.857(3) ?), the thermolysis of salt II results in a double-phase metallic powder. Original Russian Text ? S.A. Martynova, K.V. Yusenko, I.V. Korol’kov, S.A. Gromilov, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 7, pp. 541–545.     

[M(NH3)5Cl]WO4 (M = Cr, Rh): Synthesis, crystal structure, thermal properties

By single crystal X-ray diffraction the crystal structure of a series of [M(NH₃)₅Cl]WO₄ (M = Cr, Rh) complex salts is determined. The features of thermal expansion of the single crystal of [Cr(NH₃)₅Cl]WO₄ are studied by low- and high-temperature X-ray diffractometry in the temperature range from ?173°C to +127°C. It is shown that with an increase in the temperature, W-O distances and ∠O-W-O bond angles equalize and the average W-O distances decrease by 0.012 Å. The thermal properties of the salts in different gaseous atmospheres are examined and the phase composition of the obtained products is studied.     

Synthesis and crystal structure of [Cr(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>Cl][PdBr<Subscript>4</Subscript>]

A new binary complex salt — chloropentaamminechromium(III) tetrabromopalladate(II) [Cr(NH₃)₅Cl][PdBr₄] — has been synthesized. The compound was characterized by elemental, X-ray diffraction, and X-ray phase analysis. The salt is isostructural with the previously investigated compounds [M(NH₃)₅Cl][PtCl₄] (M = Ir, Rh, Ru, Co, Cr) and [CM(NH₃)₅Cl][PdBr₄] (M = Ir, Rh, Co). Crystallographic data: space group Pnma, a = 17.068(2) Å, b = 8.315(12) Å, c = 9.653(14) Å; V = 1370.0(3) ų, Z = 4, d _calc = 2.903 g/cm³.     

Synthesis, crystal structure and thermal properties of [Co(NH3)5Cl]MO4 (M = Mo, W)

Crystal structures of [Co(NH₃)₅Cl]MoO₄ and [Co(NH₃)₅Cl]WO₄ complex salts are determined by single crystal X-ray diffraction. It is demonstrated for both salts that within the temperature range T = ?123?20°C there is a negative thermal expansion (about 0.26%) towards the c axis of the orthorhombic unit cell (Pnma space group). Thermal properties of the salts are investigated. The phase composition of the products obtained on heating the salts in different gas atmospheres is studied.     

[M(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>Cl][AuCl<Subscript>4</Subscript>]Cl · <Emphasis Type="Italic">n</Emphasis>H<Subscript>2</Subscript>O (M = Rh,Ru, or Cr): Synthesis,crystal structure,and thermal properties

Double complex salts [M(NH₃)₅Cl][AuCl₄]Cl · nH₂O (M = Rh, Ru, or Cr) were synthesized and structurally studied. These compounds are isostructural; space group C2/m. Their crystal structure is built of [M(NH₃)₅Cl]²⁺ complex cations, [AuCl₄]^? complex anions, Cl^? anions, and molecules of water of crystallization. The compounds were characterized by X-ray crystallography, X-ray powder diffraction, IR spectroscopy, and thermal analysis.     

Double complex salts [Pt(NH3)5Cl][M(C2O4)3] · n H2O (M = Fe, Co, Cr): Synthesis and study

Double complexes [Pt(NH₃)₅Cl][Fe(C₂O₄)₃] · 4H₂O, [Pt(NH₃)₅Cl][Co(C₂O₄)₃] · 2H₂O, and [Pt(NH₃)₅Cl][Cr(C₂O₄)₃] · 4H₂O were synthesized and studied by single-crystal X-ray diffraction, X-ray phase analysis, differential thermal analysis, elemental analysis, and IR spectroscopy. The crystal structures of the compounds were examined from the viewpoint of the close packing of coordination polyhedra. The thermal properties of the synthesized complexes and K₃[M(C₂O₄)₃] salts (M = Fe, Co, Cr) were compared. A procedure for the synthesis of the FePt, CoPt, and CrPt intermetallic compounds through the thermolysis of the obtained complexes was developed. Original Russian Text ? K.V. Yusenko, D.B. Vasil’chenko, A.V. Zadesenets, I.A. Baidina, Yu.V. Shubin, S.V. Korenev, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52, No. 10, pp. 1589–1593.     

X-ray diffraction study of [Ru(NH3)5Cl][ReCl6] and [Ru(NH3)5Cl]2[ReCl6]Cl2 and their thermolysis products. Crystal-chemical analysis of the Ru-Re system

Binary complex salts [Ru(NH₃)₅Cl][ReCl₆] and [Ru(NH₃)₅Cl]₂[ReCl₆]Cl₂ were synthesized and characterized. An X-ray diffraction analysis showed that they were isostructural with the previously obtained isoformula salts [Rh(NH₃)₅Cl][OsCl₆] and [Ir(NH₃)₅Cl]₂[PtCl₆]Cl₂, respectively. Thermolysis of these compounds under hydrogen and helium was studied. According to X-ray phase analysis data, bimetallic solid solutions Ru_0.67Re_0.33 and Ru_0.50Re_0.50 were the final products of thermolysis. Their unit cell parameters correspond to the characteristics of alloys with similar compositions. Original Russian Text Copyright ? 2009 by S. A. Martynova, K. V. Yusenko, I. V. Korolkov, I. A. Baidina, and S. V. Korenev __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 50, No. 1, pp. 126–132, January–February, 2009.     

Structure and thermal properties of [Ir(NH3)5Cl]x[Rh(NH3)5Cl]1?xMO4 (x = 0.5, 1; M = Mo, W)

Complex salts [Ir(NH₃)₅Cl]x[Rh(NH₃)₅Cl]_1−x MO₄ (x = 0.5, 1; M = Mo, W) are synthesized and their thermal properties are studied. The crystal structures are determined for [Ir(NH₃)₅Cl]WO₄ and [Ir(NH₃)₅Cl]MoO₄. In the structures, the ions are linked by N-H...O hydrogen bonds, the shortest ones being 2.868(2)–3.422(2) ?. and 2.860(4)–3.434(3) ?. respectively. The thermal properties of the complex salts are studied in the hydrogen atmosphere and in hydrogen-helium mixtures. It is demonstrated that the final products are the mixtures of nanocrystalline powders of Ir and binary or ternary solid solutions with the hcp lattice.     

Darstellung und Kristallstruktur von (NH4)2[V(NH3)Cl5]. Die Kristallchemie der Salze (NH4)2[V(NH3)Cl5], [Rh(NH3)5Cl]Cl2 und M2VXCl5 mit M = K,NH4, Rb,Cs und X = Cl,O

Preparation and Crystal Structure of (NH₄)₂[V(NH₃)Cl₅]. The Crystal Chemistry of the Compounds (NH₄)₂[V(NH₃)Cl₅], [Rh(NH₃)₅Cl]Cl₂, and M₂VXCl₅ with M = K, NH₄, Rb, Cs and X ? Cl, O (NH₄)₂[V(NH₃)Cl₅] crystallizes like [Rh(NH₃)₅Cl]Cl₂ in the orthorhombic space group Pnma with Z = 4. The compounds are built up by isolated NH₄⁺ or Cl^? and complex MX₅Y ions. The following distances have been observed: V? N: 213.8, V? Cl: 235.8–239.1, Rh? N: 207.1–208.5, Rh? Cl: 235.5 pm. Both structures differ from the K₂PtCl₆ type mainly in the ordering of the MX₅Y polyhedra. The compounds M₂VCl₆ and M₂VOCl₅ with M = K, NH₄, Rb, and Cs crystallize with exception of the orthorhombic K₂VOCl₅ in the K₂PtCl₆ type. The ordering of the MX₅Y polyhedra in the compounds (NH₄)₂[V(NH₃)Cl₅], [Rh(NH₃)₅Cl]Cl₂ and K₂VOCl₅ enables a closer packing.     

Double complex salts with [Ru(NH3)5Cl]2+ cation and [OsCl6]2? anion: Synthesis and properties. Crystal structure of [Ru(NH3)5Cl]2[OsCl6]Cl2

Double complex salts [Ru(NH₃)₅Cl][OsCl₆] and [Ru(NH₃)₅Cl]₂[OsCl₆]Cl₂ were prepared and characterized. An X-ray diffraction study showed that [Ru(NH₃)₅Cl][OsCl₆] is isostructural to the previously synthesized [Rh(NH₃)₅Cl][OsCl₆]. The structure of [Ru(NH₃)₅Cl]₂[OsCl₆]Cl₂ was solved by X-ray diffraction (a = 11.1849(8) ?, b = 7.9528(6) ?, c = 13.4122(9) ?; β = 99.765(2)°; V= 1175.75 ?³; space group C2/m; Z = 2). Thermolysis of the compounds under hydrogen and helium was studied. According to X-ray diffraction, nanosized metallic powders of the corresponding alloys are formed as the final products of thermolysis. The compositions of the obtained solid solutions are consistent with the phase diagram of the Ru-Os system.     

Structural motifs of mixed salts Ag2[Pd(NO2)4] · Ag1-x Na x No2 x > 0.3) and [Pd(NH3)4] [MA6] (M = Re, Os, Ir, Pt; A = Cl, Br)

Mixed salts of noble metals with the general formula [Pd(NH₃)₄][MA₆], where M = Re, Os, Ir, Pt;A = Cl,Br, and Ag₂[Pd(NO₂)₄]-Ag_1-xNa_xNO₂ (x> 0.3) have been synthesized and studied by X-ray diffractometry. It was found that the former are isostructural to each other and the latter are isostructural to Na₂[Pd(NO₂)₄j-NaNO₂. The structural motif of these compounds was established and metal-metal distances were estimated by the cation sublattice method In all cases, metal atoms form common cation sublattices with lattice parameters between 4.5 and 6.3 Å. An original approach to revealing common sublattices in crystal structures where the fragments differ considerably in weight is described.     

High-temperature X-ray diffraction study of thermolysis of the double complex salt [Rh(NH3)5Cl][PtCl4]

The formation process of a nanosize powder of the equilibrium solid solution Pt_0.50Rh_0.50 by thermolysis of the double complex salt [Rh(NH₃)₅Cl][PtCl₄] under hydrogen or helium and in vacuo was studied in situ by X-ray diffraction and synchrotron radiation. The reduction temperature of the metals in the cationic and anionic moieties of the starting complex is the main factor responsible for the mechanism of solid solution formation. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1069–1073, July, 2006.     

Crystal structure of [Ir(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>Cl]<Subscript>2</Subscript>[OsCl<Subscript>6</Subscript>]Cl<Subscript>2</Subscript>. Crystal-chemical analysis of the iridium-osmium system

The [Ir(NH₃)₅Cl]₂[OsCl₆]Cl₂ binary complex salt has been prepared, and its structure was investigated by single crystal X-ray diffraction. Crystal data: a = 11.1901(13) Å, b = 7.9138(13) Å, c = 13.4384(18) Å; β = 99.640(3)°, V = 1190.0(2), space group C2/m, Z = 2, FW = 1099.47, d _x = 3.068 g/cm³. Thermolysis products of [Ir(NH₃)₅Cl]₂[OsCl₆]Cl₂, [Ir(NH₃)₅Cl][OsBr₆], (NH₄)₂[OsCl₆]_x[IrCl₆]_1?x , and K₂[OsCl₆]_x[IrCl₆]_1?x were studied by X-ray phase analysis; the unit cell parameters were refined, and the dependence of volume per atom (V/Z) on the composition of the Ir Os_1?x solid solution has been plotted.