Novel pyridyl-stabilised rigid-rod organometallic polymers and their monomeric precursors

Reaction of trans-[Pt(NC5H4CHBu2n)(2)Cl-2] 1 with an excess of HC=CR (R = Ph, C6H4Me, C6H4NO2) affords the monomeric complex trans-[Pt(NC5H4CHBu2n)(2)(C=CR)(2)] (R = Ph 2a, C6H4Me 2b, C6H4NO2 2c), the trans arrangement of the alkynyl ligands being confirmed from spectroscopic data and by an X-ray analysis of 2c;when 1 is treated with 1 equiv, of HC=CC6H2(Me)(2)C=CH the polymer [Pt(NC5H4CHBu2n)(2)C=CC6H2Me2C=C](n) is formed, which is soluble in a range of organic solvents.

Organometallic polymers: An infinite organoplatinum chain in the solid state formed by (C CH center dot center dot center dot ClPt)hydrogen bonds

The new platinum complex [PtCl[C6H2(CH(2)NMe(2))(2) -2,6-(C=CH)-4)] exhibits a polymeric linear -C=CH ... ClPt-hydrogen-bonded structure in the solid state.

Electrochemistry of Hg(II) Salts in Room-Temperature Ionic Liquids

The electrochemistry of HgCl(2) and [Hg(NTf(2))(2)] ([NTf(2)](-) = bis-{(trifluoromethyl)sulfonyl}imide) has been studied in room temperature ionic liquids. It has been found that the cyclic voltammetry of Hg(II) is strongly dependent on a number of factors (e.g., concentration, anions present in the mixture, and nature of the working electrode) and differs from that found in other media. Depending on conditions, the cyclic voltammetry of Hg(II) can give rise to one, two, or four reduction peaks, whereas the reverse oxidative scans show two to four peaks. Diffuse reflectance UV-vis spectroscopy and X-ray powder diffraction have been used to aid the assignment of the voltammetric waves.

Electrochemistry of Sulfur and Polysulfides in Ionic Liquids

The electrochemistry of elemental sulfur (S-8) and the polysulfides Na2S4 and Na2S6 has been studied for the first time in nonchloroaluminate ionic liquids. The cyclic voltammetry of S-8 in the ionic liquids is different to the behavior reported in some organic solvents, with two reductions and one oxidation peak observed. Supported by in situ UV-vis spectro-electrochemical experiments, the main reduction products of S-8 in [C(4)mim][DCA] ([C(4)mim] = 1-butyl-3-methylimidazolium; DCA = dicyanamide) have been identified as s(6)(2-) and S-4(2-), and plausible pathways for the formation of these species are proposed. Dissociation and/or disproportionation of the polyanions S-6(2-) and S-4(2-) appears to be slow in the ionic liquid, with only small amounts of the blue radical species S3(center dot-) formed in the solutions at r.t., in contrast with that observed in most molecular solvents.

Organometallic hydrogen transfer and dehydrogenation catalysts for the conversion of bio-renewable alcohols

Organometallic hydrogen transfer and dehydrogenation provide straightforward atom efficient routes from alcohols to a variety of chemical products. The potential of these reactions to enable the conversion of biomass to value added chemicals is discussed, with reference to the products that can be prepared from aliphatic alcohols in good isolated yield.

Effect of Inhibitor Compounds on N-epsilon-(Carboxymethyl)lysine (CML) and N-epsilon-(Carboxyethyl)lysine (CEL) Formation in Model Foods

The possible adverse effects on health of diet-derived advanced glycation endproducts (AGES) and advanced lipoxidation endproducts (ALES) is of current interest. This study had the objective of determining the effects of the addition of AGE/ALE inhibitors and different types of sugar and cooking oil on N-epsilon-(carboxymethyl)lysine (CML) and N-epsilon-(carboxyethyl)lysine (CEL) formation in model foods (sponge cakes). The cake baked using glucose produced the highest level of CML (2.07 +/- 0.24 mmol/mol lysine), whereas the cake baked using fructose produced the highest concentration of CEL (25.1 +/- 0.15 mmol/mol lysine). There were no significant differences between CML concentrations formed in the cakes prepared using different types of cooking oil, but significant differences (P

The comparative solvatochromism of arylazo and heteroarylazo compounds based on N,N-diethyl-m-acetylaminoaniline and N,N-diethyl-m-toluidine

Azobenzene dyes derived from various anilines and aminothiaheterocycles ate-coupled with commercially important N,N-diethyl-m-toluidine (T series) and iv,N-diethyl-m-acetylaminoaniline (A series) are positively solvatochromic. The visible spectra of 16 pairs of derivatives have been measured in up to 22 solvents, and the transition energies related to Kamlet-Taft solvent polarity parameters. In general, A-series dyes are more bathochromic than their T-series counterparts in nonpolar solvents, consistent with colour chemistry tradition, However, in more dipolar solvents the more bathochromic T-series representatives unexpectedly become more bathochromic than their A-series partners. The relative solvatochromic shifts of the A and T series are related to their respective dipole moments, These in turn are distinguished by the effect of the anilide carbonyl group dipole moment, which is antiparallel to, and thus reduces, the dipole moment of the chromogen.

Use of luminescent gold compounds in the design of thin-film oxygen sensors

The use of two gold compounds incorporated into thin plastic films as luminescence quenching oxygen sensors is described. The films are sensitive both to gaseous oxygen and to oxygen dissolved in nonaqueous media such as ethanol. The luminescence quenching of these sensors by oxygen obeys the Stern-Volmer equation and Stern-Volmer constants of 5.35 x 10(-3) and 0.9 x 10(-3) Torr(-1) are found, respectively, for the two dyes in a polystyrene polymer matrix. The sensitivity of the films is strongly influenced by the nature of the polymer matrix, and greatest sensitivity was found in systems based an the polymers polystyrene or cellulose acetate butyrate. Sensitivity was not found to be temperature dependent though raising the temperature hom 15 to 50 degrees C did result in a slight decrease in emission intensity and a hypsochromic shift in the emission wavelength. The rate of response and recovery of the sensors can be increased either by decreasing film thickness or by increasing the operating temperature. The operational and storage stability of these films is generally good though exposure to light should be avoided as one of the dyes tends to undergo photobleaching probably due to a photoinduced ligand substitution reaction.