Tetrabutylammonium Salts of Ruthenium(II) Nitroso Complexes

The paper describes synthesis of (nBu₄N)₂[RuNOCl₅](I), (nBu₄N)₂[RuNOCl₄OH](II), (nBu₄N)₂×[RuNOCl₄OH]·6H₂O (III), and (nBu₄N)₂[RuNOCl₅]· 2(nBu₄N)₂[RuNOCl₄(H₂O)]·2H₂O (IV). The complexes were studied by IR spectroscopy and powder Xray and crystal Xray analyses. The structures are built up of [RuNOCl₅]^2- (I, IV), [RuNOCl₄OH]^2- (II, III), and [RuNOCl₄(H₂O)]^- (IV) complex anions, (nBu₄N)⁺ cations, and crystal water molecules (III, IV). The substances are moderately soluble in water; highly soluble in polar organic solvents, such as acetone, ethanol, chloroform, methylene chloride; and almost insoluble in carbon tetrachloride and toluene. Under storage in light, the compounds decompose from the surface; in darkness I and II are stable, whereas III and IV can lose part of the crystal water.     

Forms of Rh(III) in Nitric Acid Solutions

The forms of Rh(III) in nitric acid solutions are studied by ¹⁴N, ¹⁵N, ¹⁷O, and ¹⁰³Rh NMR and electronic absorption spectra. At HNO₃concentrations below 5 mol/l, rhodium mainly exists as low-nuclear oligomers with a bridging fragment Rh(-OH)(-ONO₂)Rh; terminal positions of the central atoms are occupied by water molecules. It was found that the isotopic equilibrium ¹⁴NO^– ₃/¹⁵NO^– ₃of the bridging ligand sets in at an abnormally high rate, at which the isotopic exchange H₂ ¹⁷O/H₂ ¹⁶O of the terminal ligands also occurs in the dimers and trimers. The formation of low-nuclear oligomers is a common feature of Rh(III) complexes in aqueous solutions with ligand deficiency in the system. The possibility of isolating rhodium from nitric acid solutions using different methods is predicted.     

Synthesis and structure of complex compound Rh(III) of (NH4)2[Rh(NO2)3(NH3)(µ-OH)]2 composition

The crystalline structure of a new compound Rh(III) of (NH₄)₂[Rh(NO₂)₃(NH₃)(μ-OH)]₂ composition has been determined. The crystallographic characteristics are H₁₆N₁₀O₁₄Rh₂: a = 6.3963(2) Å, b = 9.3701(4) Å, c = 13.6646(5) Å, β = 102.266(1)°, V = 800.28(5) ų, Z = 2, d _calc = 2.432 g/cm³. The distance Rh...Rh in the dimer is 3.200 Å. Original Russian Text Copyright ? 2006 by S. P. Khranenko, I. A. Baidina, and S. A. Gromilov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 47, No. 2, pp. 380–384, March–April, 2006.     

[Ru(NH3)6](MoO4)Cl·3H2O and [M(NH3)6](ReO4)3·2H2O (M = Ru, Ir). Synthesis and crystal structure

X-ray crystallographic analysis is used to determine the crystal structures of [Ru(NH₃)₆](MoO₄)Cl·3H₂O and [M(NH₃)₆](ReO₄)₃·2H₂O (M = Ru, Ir) complex salts. The features of the fragment packing are studied.     

Complex salts [Pd(NH3)4](ReO4)2 and [Pd(NH3)4](MnO4)2: Synthesis, structure, and thermal properties

Complex salts, i.e., tetraamminepalladium perrhenate (I) and permanganate (II), are synthesized and studied by physicochemical methods. Their crystal structures are determined and thermal analysis is performed. The products formed in thermolysis of I and II carried out in the atmosphere of helium and hydrogen are studied. The Pd_0.33Re_0.67 solid solution based on Re is shown to form under particular temperature conditions in the atmosphere of hydrogen.     

Structural Features of Mixed Anions (Мо7 – хWхO24)6– and Their Packing in the [Pd(NH3)4]3(Мо7 – хWxO24)⋅6H2O Crystal Structure

Crystallography Reports - [Pd(NH3)4]3(Мо7 – хWxO24)?6H2O crystals with different Mo/W ratios have been formed as a result of the crystallization of a...     

Crystal structure of [Pb<Subscript>3</Subscript>(OH)<Subscript>4</Subscript>Co(NO<Subscript>2</Subscript>)<Subscript>3</Subscript>](NO<Subscript>3</Subscript>)(NO<Subscript>2</Subscript>)·2H<Subscript>2</Subscript>O

The structure of [Pb₃(OH)₄Co(NO₂)₃](NO₃)(NO₂)·2H₂O is determined by single crystal X-ray diffraction. The crystallographic characteristics are as follows: a = 8.9414(4) Å, b = 14.5330(5) Å, c = 24.9383(9) Å, V = 3240.6(2) ų, space group Pbca, Z = 8. The Co(III) atoms have a slightly distorted octahedral coordination formed by three nitrogen atoms belonging to nitro groups (Co–N_av is 1.91 Å) and three oxygen atoms belonging to hydroxyl groups (Co–O_av is 1.93 Å). The hydroxyl groups act as μ₃-bridges between the metal atoms. The geometric characteristics are analyzed and the packing motif is determined.     

Synthesis and X-ray investigation of Rb<Subscript>2</Subscript>[Pd(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>] and Cs<Subscript>2</Subscript>[Pd(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>]

Powder and single crystal X-ray diffraction studies have been performed for anhydrous nitrate complexes Rb₂[Pd(NO₃)₄] (I) and Cs₂[Pd(NO₃)₄] (II). Crystal data for I: a = 7.843(1) Å, b = 7.970(1) Å, c = 9.725(1) Å; β = 100.39(1)°, V = 597.9(1) Å ³, space group P2₁/c, Z = 2, d _calc = 2.918 g/cm³; for II: a = 10.309(2) Å, b = 10.426(2) Å, c = 11.839(2) Å; β = 108.17(3)°, V = 1209.0(4) ų, space group P2₁/c, Z = 4, d ^calc = 3.408 g/cm³. The structures are formed by isolated [Pd(NO₃)₄]^2? complex anions and alkali metal cations. The plane-square environment of the Pd atom is formed from the oxygen atoms of the monodentate nitrate groups. The geometrical characteristics of the complex anions are analyzed. Compound II has a short contact Pd...Cs 3.252 Å.