Crystal and molecular structure of nitrosyl(1,10-phenanthroline)-bis(triphenylphosphine)iridium(I) Dihexafluorophosphate, [Ir(NO)(phen)(PPh3)2][PF6]2

Summary The structure of [Ir(NO)(phen)(PPh₃)₂][PF₆]₂ has been determined from x-ray diffractometer data. The compound crystallizes in space groupPnam with four molecules in a unit cell witha = 19.924(12),b = 14.793(9) andc = 16.348(9) A. Full-matrix least-squares refinement has led to a final R value of 0.061 for the 4796 observed reflections. The structure consists of well-separated ions, and the geometry around the metal is trigonal bipyramidal with nitrosyl and bidentate 1,10-phenanthroline (in spite of the very narrow bite angle of 75.8°) ligands occupying the equatorial positions and the triphenylphosphine ligands the axial positions. The cation has an imposed crystallographicm symmetry. Important bond lengths are as follows: Ir-P, 2.391(3): Ir-N (nitrosyl) 1.700(12): Ir-N (1,10-phenanthroline) 2.103(12) and 2.142(11): N-O, 1.201(18)A. The nitrosyl ligand is linear [Ir-N-O = 179.9(9)°] so that this complex can be formulated as an NO⁺ complex of iridium(I).     

Excess enthalpies of (methyl propanoate or methyl pentanoate + 1-alkanol) at 298.15 K

The excess molar enthalpies H_m^E of methyl propanoate or methyl pentanoate + 1-butanol, + 1-hexanol, + 1-octanol, and + 1-decanol have been determined experimentally at 298.15 K using a Calvet microcalorimeter. For all these mixtures H_m^E > 0; the values increase with the chain length of the alkanol but decrease as the ester chain lengthens.     

The use of the consecutive adsorption of pyridine bases and carbon monoxide in the IR spectroscopic study of the accessibility of acid sites in microporous/mesoporous materials

A new approach to the evaluation of the accessibility of acid sites in microporous/mesoporous materials is developed and tested using a series of dealuminated mordenites. This approach is based on an IR-spectroscopic study of the consecutive adsorption of substituted alkylpyridines (pyridine, 2,4,6-trimethylpyridine, and 2,4,6-triethylpyridine) and carbon monoxide. This method allowed us to determine the strength and number of acid sites with various degrees of accessibility. The adsorption of 2,4,6-triethylpyridine on various types of materials is studied. The extinction coefficients of alkylpyridines are determined using a McBain balance placed in a cell for IR-spectroscopic measurements. Original Russian Text N.S. Nesterenko, F. Thibault-Starzyk, V. Montouilliout, V.V. Yushchenko, C. Fernandez, J.-P. Gilson, F. Fajula, I.I. Ivanova, 2006, published in Kinetika i Kataliz, 2006, Vol. 47, No. 1, pp. 45–53.     

Vapor-particle partitioning of hydrocarbons in Western Mediterranean urban and marine atmospheres

An analytical procedure is described for a comprehensive determination of the composition of hydrocarbons in the atmosphere, based on: (a) aerosol filtration and subsequent adsorption of the vapor phase onto active charcoal and polyurethane foam; (b) GPC and HPLC fractionation of the extracts, and (c) analysis of the fractions by GC-MS under EI and NICI modes. Special emphasis is placed onn-alkanes, PAHs and their oxygenated derivatives.The characterization of samples collected in a coastal urban area (Barcelona city), and far away over the Western Mediterranean, at sea level and at 1100 m of altitude, revealed significant changes in the aerosol composition, mainly attributed to initial vapor-particle partitioning processes, influenced by ambient temperature variations, and to others taking place during long-range atmospheric transport, related with the different compound photoreactivities and with an unexplained source-decoupling phenomenon.     

Studies on the metal-nuclotide (Co-5′IMP,Co-5′GMP) interaction via mössbauer emission spectroscopy and magnetic susceptibility measurements

By means of⁵⁷Co Mössbauer emission spectroscopy and magnetic susceptibility measurements, the local symmetries and electronic structure of the Co(II) ions in the Co-5IMO and Co-5GMP complexes in the hydrated and dehydrated forms have been determined.     

Oriented immobilization of Desulfovibrio gigas hydrogenase onto carbon electrodes by covalent bonds for nonmediated oxidation of H2

The orientation of hydrogenase bound covalently to a pyrolytic graphite edge electrode modified with a 4-aminophenyl monolayer can be modulated via electrostatic interactions during the immobilization step. At low ionic strength and when the amino groups of the electrode surface are mostly protonated, the hydrogenase is immobilized with the negatively charged region that surrounds its 4Fe4S cluster nearer to the protein surface facing the electrode. This allows direct electron transfer between the immobilized hydrogenase and the electrode, which is observed by the strong catalytic currents measured in the presence of the H2 substrate. Therefore, a very stable enzymatic electrode is produced that catalyzes nonmediated H2 oxidation.     

SOLVENT EFFECTS ON THE TAUTOMERIZATION OF 5′-DEOXYPYRIDOXAL. A PHOTOPHYSICAL STUDY

Abstract— Absorption and fluorescence spectra of 5′-deoxypyridoxal (DPL) in various pure solvents and mixtures were recorded both at room temperature and over the range10–65°C. The areas under the absorption bands were analyzed to obtain the mole fraction (f_N, f_z) of two tautomers (the zwitterionic, Z, and neutral, N, forms) in the ground state. The following spectral parameters were determined from the fluorescence spectra: Stokes shift (Δv), fluorescence quantum yield of the neutral form (Q_N), fluorescence ratio of the neutral to the zwitterionic form (ø_N/ø_Z) and the rate constant of tautomerization (k₁) from Z to N in the excited state. Some of these parameters (f_N, Δv, Q_N, k₁) were found to depend on the proton donor character of the solvent, whereas others (ø_N/ø_Z) depended on its dipole moment. Thus, the absorption and fluorescence spectra of DPL allow one to obtain information on the polarity and the concentration of –OH groups on its environment.     

A molecular orbital study of trans-polyenes to 18 double bonds

Calculations involving molecular orbitals have appeared in the chemical literature over the past few years, but all have used smalltrans-polyenes. We now report extended Huckel molecular orbital calculations ontrans-polyenes of up to 18 double bonds (36 carbons and 38 hydrogen atoms). Information obtained from these calculations include total energies, bond gaps, and net charges on each atom. Also found is that the band gap approaches 1.41 eV as the number of double bonds approaches infinity. This value is quite close to reported experimental values. Data are also presented for polyenes assuming equal C-C bond lengths.