A. V. Il'yasov

Some electrochemically generated elemento-organicradical ions and metal complexes as studied by esr

Abstract ESR spectra have been obtained for the radical anions Ph n El XXX , where El = P, Si or As, and also for substituted nitrobenzenes. Radical anions were generated by electrochemical reduction within a microwave cavity. The nature and stability of radical ions and other paramagnetic species were established by the investigation of the electrochemical behaviour of the substances. The spin density distribution shows that atoms of the elements in Ph n El XXX are not to be taken as “isolating bridges”. Spin density distributions have also been established for other radical ions. Paramagnetic complexes Mo V and W V have been prepared by electrochemical reduction of appropriate molybdenum and tungsten compounds and their structure and magnetic parameters have been established.

Diethylarsine benzoate radical anions

1. Arsinobenzoates are reduced in three steps, the first of which involves one electron and is reversible. The diethylarsinyl groups are electron acceptors. Transfer of a second electron leads to the rupture of the As-C bond and to the formation of methyl benzoate. 2. The spin-density distribution in the arsinobenzoate radical anions has been studied.

EPR spectra of photo- and electrochemically generated hydrazyl radicals

Hydrazyl radicals are formed from triarylhydrazines either by UV irradiation or by electrochemical oxidation in the presence of bases. Here high resolution EPR spectra are observed, in which the hyperfine structure from all of the magnetic nuclei is manifested.

Electrochemically generated free radicals: Communication 1. Reduction of carboxylic acid derivatives

1. The mechanism of the polarographic reduction of nitrophenyldiethylarsines, their oxides and sulfides in aprotonic medium was studied. Schemes of the subsequent chemical reactions after the reception of a second electron by these systems were proposed. 2. New organoarsenic anion radicals were produced by electrochemical reduction and investigated by the ESR method. Their stability was estimated. The delocalization of the unshared electron in them was studied, and possible causes of the appreciable decrease in the spin density on the arsenic atom in the transition from anion radicals with a tetra-to a tricoordinated arsenic atom were considered.