Electrochemical reduction of CO in an aqueous media was studied with voltammetric and coulometric measurements. The reduction did not proceed at Au and Pt electrodes. CO is appreciably reduced at Cu to hydrocarbons. Ni yielded products to some extent. The reaction was discussed in terms of the adsorption of CO or related intermediate species on the electrode.
Adducts of ruthenocene derivatives with Lewis acids (HgCl2, SnCl4, and I2) were studied by means of 13C-CP-MAS NMR spectroscopy and other physicochemical techniques. Large low-field shifts found in the 13C-CP-MAS NMR spectroscopy suggest the presence of a direct chemical bonding between the ruthenium and the Lewis acids.
A dinucleating macrocycle with dissimilar coordination sites (imine and amide sites), 12,24-dihydroxy-1,6-dioxo-2,5,14,17-tetra-aza[6·6]metacyclophane-13,17-diene, has been obtained and its complexing behavior was examined. It forms both mononuclear and dinuclear complexes with nickel(II) ion but only dinuclear complex with copper(II) ion. In the mononuclear nickel(II) complex the metal ion is bound at the imine site. In the dinuclear copper(II) complex an antiferromagnetic spin-exchange interaction (J=−355.2 cm−1) occurred through the bridging phenolic oxygens.
Deep purplish red semicrystaline precipitates were obtained by the treatment of Cu2O with HF. After calcination at 100 °C or higher temperature, this compound was successfully used as a highly effective halogen-exchange fluorination reagent for primary alkyl halides in the presence of pyridine derivatives. AgF and a mixture of CuF2 with copper powder also exhibited high activity in the reaction.
Title annulenes have been synthesized through a double Wittig reaction between the vinylogous dicarbaldehydes of 1,6-diformylcycloheptatriene and bis[(triphenylphosphonio)methyl]sulfide dibromide, and their 1H NMR spectra were examined proving that the thia- and - annulenes sustain ring current, while the thia-annulene does not.
Reduction of 1,1′-trimethylenebis(pyridinium) dibromide with sodium amalgam produces the cyclomers of 1,1′-trimethylene-bis(pyridinyl) diradical. Meso and dl forms of the cyclomers are convertible to each other. Two conformations of the diradical are observed in the triplet ESR spectrum at 77 K.