D. A. Piryazev

Mixed-ligand cluster [Mo 3 S 4 (Dtp) 2 (μ-AcO)Cl(Me 2 Bipy)]: Synthesis and structure

Mixed-ligand cluster [Mo3S4(Dtp)2(μ-AcO)Cl(Me2Bipy)] · CHCl3 (I · CHCl3), where Dtp is (EtO)2PS2, was synthesized by the reaction of the molybdenum aqua complex [Mo3S4(H2O)9]4+ with 4,4′-dimethyl-2,2′-bipyridine (Me2Bipy) and phosphorus sulfide (P4S10) in ethanol followed by chromatographic separation on silica gel and crystallization in the presence of acetic acid. The crystal structure of I · CHCl3 was determined by X-ray diffraction analysis. The synthesized compound was characterized by the IR and NMR spectra and elemental analysis. The electronic structure of the synthesized compound was established, and its electrochemical behavior in a solution was studied.

Synthesis, crystal structure, and luminescence properties of complexes (4-ViBnNMe3)2[{M6(µ3-I)8}I6] (M = Mo, W; (4-ViBnNMe3)+ is trimethyl(4-vinylbenzyl)ammonium)

Two new compounds based on octahedral molybdenum and tungsten iodide cluster complexes of the composition (4-ViBnNMe3)2[{M6(µ3-I)8}I6] (M = Mo, W; (4-ViBnNMe3)+ is trimethyl(4-vinylbenzyl)ammonium) were synthesized and structurally characterized. The luminescence properties of powder samples of the synthesized compounds and of the salts (Bu4N)2[{M6(µ3-I)8}I6] described earlier were investigated. Due to the presence of the vinylcontaining cation, these compounds can be involved in radical copolymerization in order to produce polymeric luminescent materials.

Spin crossover in heteroligand iron(II) complexes with iris(3,5-dimethylpyrazol-1-yl)methane

Heteroligand iron(II) complexes with tris(3,5-dimethylpyrazol-1-yl)methane (HC(3,5-Me2Pz)3) are synthesized. Along with this ligand, the internal coordination sphere of Fe(II) of the new complexes includes other nitrogen-containing heterocycles, in particular, tetrazole (Tz), pyrazole (Pz), 3,5-dimethylpyrazole (3,5-Me2Pz), and 3-amino-4-ethoxycarbonylpyrazole (Ametcpz), as well as ions NCS− or N(CN)2−. Compounds [Fe(HC(3,5-Me2Pz)3)(Tz)3](NO3)2 (I), [Fe(HC(3,5-Me2Pz)3)(Tz)3](ClO4)2 (II), [Fe(HC(3,5-Me2Pz)3)(Pz)3](NO3)2 (III), [Fe(HC(3,5-Me2Pz)3)(Aecpz)(NCS)2] (IV), and [Fe(HC(3,5-Me2Pz)3)(3,5-Me2Pz)(N(CN)2)2] · 0.5H2O (V) are isolated. The study of the temperature dependence μeff(T) shows the spin crossover 1A1 ⇔ 5T2 accompanied by thermochromism (the color changes from white to pink) in complexes I, II, and IV. The molecular and crystal structures of complex V are determined by X-ray diffraction analysis (CIF file CCDC 994626).

Crystal structure and thermal properties of (1,1,1,5,5,5-hexafluoropentanoato-4)··(dicarbonyl)iridium(I)

The Ir(CO)2(hfac) complex (hfac = CF3C(O)CHC(O)CF3) has been studied by X-ray crystallographic analysis. The crystallographic data are as follows: space group Cmc21, a = 8.680(4) Å, b = 18.951(1) Å, c = 6.491(3) Å, V = 1067.7(8) Å3, Z = 4, R = 0.0327. The structure is molecular; the coordination polyhedron of iridium adopts a distorted square geometry. The average Ir–O and Ir–C distances are 2.06(1) Å and 1.82(4) Å respectively. The OIrO and CIrC angles are nearly equal (88.7(5)° and 89(1)° respectively). The thermal properties of the complex have been studied by thermogravimetry.

Structure and thermal properties of the molybdenum complex Mo(acac)3

A method for the synthesis of the Mo(acac)3 complex is proposed and its crystal structure is determined by single crystal X-ray diffraction. Space group P21/c, a = 19.7538(5) Å, b = 7.4821(2) Å, c = 34.6190(8) Å, β = 96.8055(12)°, V = 5080.6(2) Å3, Z = 12. The compound is studied by the thermogravimetric analysis, and MoO3 is shown to be the result of its decomposition.

Synthesis, some properties, and crystalline modifications of fac-[Ru(NO)(Py)2Cl3]

According to the data of 1H NMR spectroscopy, trans-hydroxochloro complexes containing from two to four pyridine molecules in the internal sphere are formed on the heating of a dilute aqueous solution of K2[Ru(NO)Cl5] with pyridine. The evaporation of the reaction solution with concentrated hydrochloric acid gives fac-[Ru(NO)(Py)2Cl3] (I) in a yield of ~90%. The structures of two crystalline modifications of this complex are determined by X-ray diffraction analysis (CIF files ССDС nos. 1452208 (Ia) and 1452207 (Ib)). IR spectroscopy shows that the irradiation of complex I (λ ~ 450 nm, T = 80 K) results in photoisomerization with the formation of the metastable state MS1 in which the nitroso group is coordinated by the oxygen atom. The activation parameters of the photoisomerization are determined from the data of differential scanning calorimetry (DSC). Compound trans-[Ru(NO)Py4(OH)]Cl2 ∙ H2O is isolated in a yield of ~70% on reflux of complex I with a pyridine excess in an aqueous solution, and the presence of molecules of water of crystallization in this compound is confirmed by thermal gravimetry (TG) and IR spectroscopy.

New trinuclear μ3-vinylidene cluster CpReFePt(μ3-C=CHPh)(CO) 5 [P(OPr i ) 3 ] 2

The X-ray diffraction study of a new heterometallic cluster CpReFePt(μ3-C=CHPh)(CO)5[P(OPri)3]2 is performed. The crystallographic characteristics are as follows: a = 11.0275(4) Å, b = 33.0367(12) Å, c = 12.2691(5) Å, β = 98.3660(10)°, V = 4422.2(3) Å3, space group P21/n, Z = 4, dcalc = 1.744 g/cm3. The cluster contains the phenylvinylidene ligand coordinated with a trimetallic core in the form of a Re–Fe–Pt chain (the Re–Fe and Fe–Pt bond lengths are 2.794(7) Å and 2.628(1) Å respectively; the Re···Pt distance is 3.354(1) Å).

Crystal and molecular structure of [Au(C14H22N4)]ReO4

Perrhenate of the tetraazamacrocyclic complex of gold(III) [Au(C14H22N4)]ReO4 is synthesized. The crystal structure of the compound is determined by single crystal X-ray diffraction. The crystallographic data are as follows: а = 7.733(2) Å, b = 11.368(2) Å, c = 11.685(2) Å, α = 116.23°, β = 104.26°, γ = 94.96°; V = 870.3(3) Å3, space group P(–1), Z = 2, dcalc = 2.647 g/cm3, R = 0.0245. The packing of the complex is comprised of double stacks of cations and chains of anions linked into two-dimensional layers due to weak intermolecular interactions (non-classical hydrogen bonds C–H…O, C–H…Au, C–H…π and the Au…Au contacts). The thermal decomposition of the obtained compound in the hydrogen atmosphere is studied. According to the powder X-ray diffraction data, the product of the reduction of the synthesized salt is a mixture of nanocrystalline phases of Re and Au with the coherent-scattering regions of 17 nm and 13 nm respectively.

Synthesis of Im3[Mo3(μ3-S)(μ-S2)3Br6]Br (Im = 1-ethyl-3-methylimidazolium) in Ionic Liquid: A New Way of Breaking Up Chalcogenide Cluster Coordination Polymers

Abstract Reaction of 1D cluster coordination polymer Mo3S7Br4 with an ionic liquid composed of 1-ethyl-3-methylimidazolium bromide (ImBr) and AlBr3 in 2:1 molar ratio affords Im3[Mo3(μ3-S)(μ-S2)3Br6]Br (1) in high yield. X-ray structure of 1·CH3CN is reported.Graphical Abstract

Syntheses and structures of the cobalt, nickel, and zinc complexes with 1,4-diaza-1,3-butadiene ligands

Several cobalt(II), nickel(II), and zinc(II) complexes with a series of ligands of the 1,4-diaza-1,3-butadiene type bearing aryl (2,6-di-iso-propylphenyl, mesityl) and alkyl (tert-butyl, iso-propyl) substituents at the nitrogen atoms are synthesized. The obtained complexes are characterized by X-ray structure analysis, IR spectroscopy, and elemental analysis.