Cis-coordination of the chromate anions in helical Co/Ni block-type polymeric systems. Structural and spectroscopic characteristics of catena(μ-CrO4-O,O′)[Co(HIm)3H2O] and catena(μ-CrO4-O,O′)[Co0.43Ni0.57(HIm)3H2O]

Two polymeric complexes: catena(μ-CrO₄-O,O′)[Co(HIm)₃H₂O] (1) and catena(μ-CrO₄-O,O′)[Co_0.43Ni_0.57(HIm)₃H₂O] (2) (where HIm=imidazole) with a cis-bridging coordination mode of the CrO₄ ²⁻ anion have been synthesized and characterized by X-ray and spectroscopic methods. These crystals were isolated from nine systems of varying reagent molar ratios and three excluding anions: Cl⁻, NO₃ ⁻ and SO₄ ²⁻ exclusively as mer [M(HIm)₃O₃]-type isomers. The unit cell of these isostructural complexes (monoclinic crystal system P2₁ /n) contains two independent helixes, left- and right handed, stabilized by intrahelical and interhelical hydrogen bonding and π–π interaction between pairs of the imidazole rings from neighbouring helixes. The Raman spectra at 77 K of 1 and 2 deconvoluted into lorentzian components revealed the block-type polymeric structure of the complexes. Moreover, the solution studies at millimolar concentrations of 1 and 2 indicated their complete decomposition in water. Four K electronic spectral analysis of the crystals (band deconvolution into gaussian components) enhanced with the data obtained in the polarized light allowed for assignment of the bands to the respective d–d transition (D_4h symmetry). It was found that the metallic centres are independently absorbing species, which supports the suggestion of a block-type structure of the polymers. The respective crystal field parameters for Co and Ni were calculated.     

Enhancing selectivity in oxidation catalysis with sol-gel nanocomposites

Valuable organic compounds such as alpha-hydroxy acids are easily synthesised with relevant selectivity enhancement using a sol-gel hydrophobized nanostructured silica matrix doped with the organocatalyst TEMPO: A materials science based synthetic route which cannot be achieved via classical homogeneous synthesis.     

Studies on the reactivity of phenyliodonium ylide of 2-hydroxy-1,4-naphthoquinone: reactions with indole derivatives and other C-nucleophiles

[reaction: see text] Thermal decomposition of phenyliodonium ylide of 2-hydroxy-1,4-naphthoquinone (lawsone) in the presence of indole derivatives affords 3-acylated indoles existing in their enol forms, through a ring contraction and alpha,alpha'-dioxoketene formation reaction. The same reactants afford 3-(3-indolyl)-2-hydroxy-1,4-naphthoquinones in a copper-catalyzed reaction. Enamines, among other C-nucleophiles tested, give analogous results.     

Vilsmeier formylation of 5,10,15-triphenylcorrole: expected and unusual products

5,10,15-Triphenylcorrole (1) reacts with the Vilsmeier reagent (POCl(3)/DMF) to give the corresponding 3-formyl derivative 3 as the major product. The regioselectivity of the reaction was proven by X-ray crystallography and only traces of the 2-formyl isomer were observed. A more polar product is also observed and this compound becomes the major product when an excess of DMF is used for the preparation of the Vilsmeier reagent, while the formation of the 3-formyl isomer is almost completely suppressed. X-ray crystallography allowed us to identify this compound as the fully substituted N-ethane bridged derivative 4, formed from the attack of the Vilsmeier reagent at the inner core of the macrocycle. This compound is unique among porphyrinoid macrocycles, and further confirms the peculiarity of corrole chemistry.     

The interphase between mercury and acetone+ nitromethane mixtures with KPF6 as a supporting electrolyte

Differential capacity and interfacial tension measurements were carried out on mercury for acetone+nitromethane mixtures with KPF₆ as a supporting electrolyte. On the basis of Gibbs adsorption equation and Guggenheim's model of the surface phase the composition of the surface layer was estimated for different acetone contents and different charges on the mercury electrode. The results obtained indicate that the positive acetone adsorption is marked at negative charges with maximum at σ_m=?0.07 C m^?2, but is practically non-existent at zero and positive charges.     

Excess thermodynamic properties of the 2-propanol + dichloromethane system at 25°C

Densities, viscosities, enthalpies, vapor-liquid equilibria, and surface tensions were determined at 25°C for the 2-propanol+dichloromethane system. From the experimental results excess volumes, viscosities, enthalpies, Gibbs energies, and excess surface tensions were calculated. An attempt has been made to explain the observed deviations from ideal behavior on the basis of intermolecular interactions.     

The behaviour of stereoisomeric ions in the gas phase: 2—Negative and positive chemical ionization of cyclohexanehexacarboxylic methyl esters

The positive ion chemical ionization (CI (isobutane)), negative ion chemical ionization (NICI) electron attachment (CH₄, He) and NICI (OH^?) spectra of the title compounds have been studied in detail with the aid of deuterium-labelled derivatives. The obtained results show that under CI conditions the stereospecificity is retained. Interesting correlations with the condensed phase epimerization yields are emphasized.     

Ab initio study of the cyclooctatetraenyl radical

Ab initio calculations have been carried out on the 1,3,5,7- and 1,2,4,7-tetraene configurations of the cyclooctatetraenyl radical at UHF, ROHF, MCSCF, ROCISD, QCISD, and CCSD(T) levels of theory with 6-311G(d,p) and cc-pVDZ basis sets. Although spin contamination is present, the ROCISD calculations support the energies obtained from less intensive, UHF-based coupled cluster calculations over the energies obtained from MCSCF analysis of the pi-electron orbitals. The 1,3,5,7-form is a local minimum at the coupled cluster levels, higher in energy than the resonance-stabilized 1,2,4,7-form by 10-13 kJ/mol, but bounded by a barrier of less than 0.5 kJ/mol. The isomerization surface connecting these two structures is described and results reported from integration of the vibrational Schr?dinger equation on that surface. Excited vibrational states at energies just above the isomerization barrier are dominated by the character of the 1,3,5,7-tetraenyl radical, which suggests that chemistry involving this intermediate at typical combustion temperatures may branch at this juncture.     

pH controls the rate and mechanism of nitrosylation of water-soluble FeIII porphyrin complexes

In-depth kinetic and mechanistic studies on the reversible binding of NO to water-soluble iron(III) porphyrins as a function of pH revealed unexpected reaction kinetics for monohydroxo-ligated (P)Fe(III)(OH) species formed by deprotonation of coordinated water in diaqua-ligated (P)Fe(III)(H(2)O)(2). The observed significant decrease in the rate of NO binding to (P)Fe(OH) as compared to that of (P)Fe(H(2)O)(2) does not conform with expectations based on previous mechanistic work on NO-heme interactions, which would point to a diffusion-limited reaction for the five-coordinate Fe(III) center in (P)Fe(OH). The decrease in rate and an associatively activated mode of NO binding observed at high pH is ascribed to an increase in the activation barrier related to spin state and structural changes accompanying NO coordination to the high-spin (P)Fe(III)(OH) complex. The existence of such a barrier has previously been observed in the reactions of five-coordinate iron(II) hemes with CO and is evidenced for the first time for the process involving coordination of NO to the iron heme complex. The observed reactivity pattern, relevant in the context of studies on NO interactions with synthetic and biologically important hemes (in particular, hemoproteins), is reported here for an example of a simple water-soluble iron(III) porphyrin [meso-tetrakis(sulfonatomesityl)porphinato]-iron(III), (TMPS)Fe(III).     

Gas–liquid partition coefficients and Henry's law constants of methyl mercaptan in aqueous solutions of Fe(II)–CDTA chelate complex

Utilization of ferric chelate complex of trans-1,2-cyclohexanediaminetetraacetic acid (CDTA) for the oxidative scrubbing of H₂S and CH₃SH in Kraft mill streams can be beneficial from the standpoints of iron protection against precipitation and oxygen-mediated regenerative oxidation of the ferrous chelate CDTA. The physical solubility of methyl mercaptan in CDTA–Fe(III) complex cannot be measured directly because of oxidation of the sulfur-bearing gaseous species with the ferric chelate. Therefore, this investigation was carried out to determine the gas–liquid partition coefficients and Henry's law constants of methyl mercaptan in aqueous iron-free CDTA solutions and non-reacting ferrous chelate solutions (CDTA–Fe(II) complex), using the static headspace method with an estimated accuracy of about 2%. Experiments with aqueous solutions of chelate concentrations varying between 38 and 300 mol m⁻³ were carried out at temperatures between 298 and 333 K and atmospheric pressure. It was shown that the methyl mercaptan solubility decreases with increasing temperature for all systems but was not much influenced, in the studied conditions, by the chelate concentration especially at larger temperatures.