Vyacheslav A. Emelyanov

Variety of molecular conducting layers in the family of radical cation salts based on BEDT-TTF with the metal mononitrosyl complex [OsNOCl5]2−

Four new BEDT-TTF radical cation salts with the [OsNOCl5]2− anion have been synthesized: α′-(BEDT-TTF)4[OsNOCl5]·C6H5NO2 (1), δ-(BEDT-TTF)4[OsNOCl5]1.33·(C6H5NO2)0.67 (2), κ-(BEDT-TTF)4[OsNOCl5]·C6H5CN (3) and β-(BEDT-TTF)2[OsNOCl5] (4). The salts were characterized by single-crystal X-ray diffraction, electrical resistance measurements, and electronic band-structure calculations. Evidence for commensurate structural modulations was found for 2 and 3. The crystals of 1, 3 and 4 are semiconductors while those of 2 exhibit a metal-to-insulator transition around 160 K. Analysis of the correlation between the crystal structure, transport properties and electronic structure of these and related salts suggests the possibility of smoothly changing the conductivity of κ-phases with two types of donors and dimers from semiconducting to metallic as well as the need to reconsider the origin of the metal-to-insulator transitions of δ-type salts.

Synthesis and crystal structure of trans-nitrosoaquatetraammineruthenium(II) sulphate hydrosulphate, [Ru(NO)(NH3)4(H2O)](SO4)(HSO4)

Abstract The reaction between [RuNO(NH 3 ) 4 OH]Cl 2 and an excess of 2 M H 2 SO 4 leads to the protonation of the starting complex and crystallisation of the title complex with sulphate and hydrosulphate anions. The crystal structure of the product has been determined. The linear nitroso group and water molecule are coordinated in trans positions.

Tetrabutylammonium Salts of Ruthenium(II) Nitroso Complexes

The paper describes synthesis of (n‐Bu4N)2[RuNOCl5](I), (n‐Bu4N)2[RuNOCl4OH](II), (n‐Bu4N)2×[RuNOCl4OH]·6H2O (III), and (n‐Bu4N)2[RuNOCl5]· 2(n‐Bu4N)2[RuNOCl4(H2O)]·2H2O (IV). The complexes were studied by IR spectroscopy and powder X‐ray and crystal X‐ray analyses. The structures are built up of [RuNOCl5]2- (I, IV), [RuNOCl4OH]2- (II, III), and [RuNOCl4(H2O)]- (IV) complex anions, (n‐Bu4N)+ 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.

Two Oxygen-Coordinated Metastable Ru–ON States for Ruthenium Mononitrosyl Complex

The properties of Ru-ON states were studied in cis-[RuNO(NH3)2(NO2)2OH] under illumination. The structure contains two nonequivalent complexes, and the metastable state was generated for both molecules with 19(1) and 31(1)% populations. The MS1 thermal decay occurs as a one-step process at about 240 K according to differential scanning calorimetry (DSC). For the first-order reaction, the frequency factor and activation energy for the decay process were determined as 2.0(2) × 10(13) s(-1) and 68.3(4) kJ mol(-1), respectively. Also, the simultaneous metastable state decay observed via DSC was in agreement with IR spectroscopy.

Synthesis and Crystal Structure of Nitrosoruthenium Triammino Complex [RuNO(NH3)3Cl(H2O)]Cl2

This paper reports on a procedure for the synthesis of the compound [RuNO(NH3)3Cl(H2O)]Cl2. The complex was studied by IR spectroscopy and X-ray phase and X-ray diffraction analyses. Crystal data for RuCl3N4O2H11: a = 13.151(2), b = 6.852(1), c = 10.361(1) Å, V = 933.6(2) Å2, space group Pna21, Z = 4, dcalc = 2.181 g/cm3, dexp = 2.178 g/cm3. The structure consists of the [RuNO(NH3)3Cl(H2O)]2+ complex cations and Cl– anions. The compound crystallizes as small orange red isometric orthorhombic crystals well soluble in water and insoluble in concentrated hydrochloric acid and organic solvents and is stable when stored in air.

Synthesis and crystal structure of sodiumtrans- nitrosoaquatetrachlororuthenate(II)

Synthesis of the compound NalRuNOCl4H2O] . 2H2O is reported. The complex was investigated by IR spectroscopy and X-ray phase and diffraction analyses. Crystal data: a = 7.0103(7), b = 11.133(1), c = 12.843(1) Å, β = 99.076(8)ℴ, V = 989.8(2) Å3, space group P2l/n, 2 = 4, dcalc = 2.348, dexp = 2.340 g/cm3. The structure consists of [ RUNOCI4H2O] complex onions, Na+ cations, and crystallization water molecules. The compound crystallizes as dark red concretions formed after prolonged storage of a saturated aqueous solution. The crystals are hygroscopic and spread when stored in air.

Formation of a Dimer with a Double Hydroxo Bridge in Nitric Acid Solutions of the Nitrosotetranitrohydroxo Complex of Ruthenium(II). Crystal Structure of K2[RuNO(NO2)3(μ-OH)]2

AbstractFine yellowish orange crystals of the binuclear complex K2[RuNO(NO2)3(μ-OH)]2 were obtained by the reaction of K2[RuNO(NO2)4OH] with a stoichiometric amount of 0.8 M nitric acid at room temperature. The compound was investigated by IR spectroscopy, X-ray phase analysis (DRON-3M, CuKα radiation), and X-ray diffraction analysis (Nonius CAD-4, MoKα radiation, graphite monochromator, ω scan mode, 1406 reflections). The crystals are poorly soluble in water and practically insoluble in ethanol and acetone; the compound is stable when stored in air. Crystal data for H2K2N8O16Ru2 are: a = 8.596(2), b = 10.111(1), c = 9.537(1) Å, β = 104.42(1)°, V = 802.8(2) Å3, space group

Synthesis and crystal structures of lithium and potassium hexanitroruthenates (II)

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