Reaction of the [B<Subscript>10</Subscript>H<Subscript>9</Subscript>O<Subscript>2</Subscript>C<Subscript>4</Subscript>H<Subscript>8</Subscript>]<Superscript>–</Superscript> anion with C-nucleophiles

The reactions of 1,4-dioxane-substituted closo-decaborate anion ([B₁₀H₉O₂C₄H₈]^–) with metal acetylenides, diethyl malonate, ethyl acetoacetate, triethyl orthoformate, acetylacetone, and malonodinitrile were studied. The reactions were shown to be accompanied with substituent ring opening and attachment of the corresponding pendant functional group. The obtained compounds were characterized by various physicochemical methods (IR and polynuclear NMR spectroscopy, ESI mass spectrometry).     

Copper(II), nickel(II), and zinc(II) complexes with <Emphasis Type="Italic">o</Emphasis>-tozylaminobenzaldehyde 4,6-dimethylpyrimidyl hydrazone

o-Tosylaminobenzaldehyde dimethylpyrimidyl hydrazone and its copper(II), nickel(II), and zinc(II) complexesare synthesized and studied. According to the X-ray diffraction data, the zinc(II) complex has the structure of a tetragonal pyramid with the N₃O donor ligand environment. According to EPR and magnetochemistry data, the copper(II) complex has a similar structure of the chelate core. In the nickel(II) complex, the solvent molecule completes the coordination core to an octahedron.     

Synthesis,structure, and optical properties of iridium(III) complex with 1-benzyl-2-phenylbenzimidazole and 4,4'-dicarboxy-2,2'-bipyridyne

A new cyclometalated iridium(III) complex [Ir(L)₂(Hdcbpy)] (1) has been synthesized, where L is 1-benzyl-2-phenylbenzimidazole and Hdcbpy is monoprotonated 4,4′-dicarboxy-2,2′-bipyridine. The structure of complex 1 has been determined by X-ray diffraction. The optical properties of complex 1 have been studied, and the quantum yield of luminescence has been measured.     

Modeling of the composition of the eutonic solution in the NaCl–AlCl<Subscript>3</Subscript>−SrCl<Subscript>2</Subscript>–HCl–H<Subscript>2</Subscript>O system at 25°С and its experimental confirmation

The solubility was studied in the system NaCl–AlCl₃?SrCl₂–HCl–H₂O of the eutonic type at 25°C in the section 28 wt % HCl. It was determined that it is possible to derive equations of the solubility surface of crystallizing salts and to calculate the composition of the eutonic solution.     

Study of lithium complexes with benzo-15-crown-5 ether by X-ray diffraction and IR spectroscopy

The complex formation of lithium with benzo-15-crown-5 (B15C5) was investigated. The complexes LiB15C5H₂OX, where X = Cl^? (1), I^? (2), (3), (5), and LiBF₄B15C5 (4) were synthesized and studied by IR spectroscopy. Complexes 1–4 were examined by X-ray diffraction. According to IR spectroscopy data, the crown ether conformation changes upon dissolution. The interaction of the extracted complex with the solvent was identified.     

Selective precipitation of rare earth orthophosphates with hydrogen peroxide from phosphoric acid solutions

It has been shown for the first time that the use of hydrogen peroxide allows precipitation of rare earth orthophosphates (La–Tb) from phosphoric acid solutions at temperatures below 100°C. Either anhydrous or hydrated orthophosphates with monazite or rhabdophane structure, respectively, can be obtained depending on rare earth element position in lanthanide series and precipitation conditions (orthophosphoric acid and hydrogen peroxide concentration). Hydrated orthophosphates with rhabdophane structure can be prepared by precipitation with hydrogen peroxide for all studied rare earth elements.     

Substituted benzotriazoles as inhibitors of copper corrosion in borate buffer solutions

The adsorption of substituted 1,2,3-benzotriazoles (R-BTAs) onto copper is measured via ellipsometry in a pure borate buffer (pH 7.4) and satisfactorily described by Temkin’s isotherm. The adsorption free energy (?ΔG _a ⁰ ) values of these azoles are determined. The (?ΔG _a ⁰ ) values are found to rise as their hydrophobicity, characterized by the logarithm of the partition coefficient of a substituted BTA in a model octanol–water system (logP), grows. The minimum concentration sufficient for the spontaneous passivation of copper (C _min) and a shift in the potential of local copper depassivation with chlorides (E _pt) after an azole is added to the solution (i.e., ΔE = E _pt ⁱⁿ ? E _pt ^backgr characterizing the ability of its adsorption to stabilize passivation) are determined in the same solution containing a corrosion additive (0.01М NaCl) for each azole under study. Both criteria of the passivating properties of azoles (logC _min and ΔE) are shown to correlate linearly with logP, testifying to the role played by surface activity of this family of organic inhibitors in protecting copper in an aqueous solution.     

5,15-bis(4′-methoxyphenyl)-3,7,13,17-tetramethyl-2,8,12,18-tetraethylporphin axial complexes of rhenium: Synthesis and reactions in protic solvents

The spectral (UV–Vis, IR, and NMR ¹H) properties and the state of oxorhenium(V) complexes with 5,15-bis(4′-methoxyphenyl)-3,7,13,17-tetramethyl-2,8,12,18-tetraethylporphin H₂P (O=Re(X)P) in protic solvents have been studied depending on the axial trans-ligand X^– (X = Cl, OPh, or OH). The O=Re(Cl)P, O=Re(OPh)P, and O=Re(OH)P in AcOH and CF3COOH are subjected to reaction of substitution their axial ligands with solvent molecules or anions, while remaining stable to the dissociation of M–N bonds and to oxidation both to the macrocyclic ligand and to the central metal cation. Quantitative parameters of the coordination of molecular oxygen by O=Re(Cl)P in 17.4–18.2 M H₂SO₄ to form O=Re(O₂)P⁺ · Cl^– have been obtained, these parameters being independent of the initial H₂SO₄ concentration. The character of peripheral functional substituents in H₂P has been shown to be responsible for the stability of the studied oxo complexes to chemical oxidation in aerated acids.     

Site-selective Csp3-H aryloxylation of natural product Tanshinone IIA and its analogues

A novel catalyst-free Csp³-H aryloxylation approach allowing for rapid installation of a wide range of aryloxyl groups regioselectively at the C-4 position of Tanshinone IIA under simple and mild conditions was developed. This unique protocol exhibited atom-/step-economy, low cost, high efficiency and robust functional-group tolerance, which will greatly facilitate to diversify the A-ring of the bioactive natural product.     

Metal-free and selective cleavage of unstrained carbon–carbon single bonds: Synthesis of β-ketosulfones from β-chlorohydrins and sodium sulfinates

A metal-free protocol for the selective cleavage of unstrained C–C single bonds was developed. Under the catalysis of KI and in the presence of NaHCO₃, the readily available α-chloro-β-hydroxy ketones underwent bond breaking and sulfonylation smoothly to afford β-ketosulfones with high efficiency and broad substrate scope. Mechanism investigations, both experimental and theoretical, showed that a retro-aldol cleavage/nucleophilic substitution sequence might be involved.