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TRIS 2,4,6-TRIMETHYLPHENYL-PHOSPHINE AND ARSINE RADICAL CATIONS

Abstract The character of electrochemical oxidation of trimesitylphosphine and trimesitylarsine in acetonitrile has been studied on the rotating platinum electrode. Their oxidation has been shown to involve two stages, the first one being the one-electron reversible wave. Characteristics of common anodic and cathodic waves of degassed solution of substances on stationary electrodes and symmetry of their cyclic voltammetry polarograms indicate the stability of radical cations formed. Electrochemically generated radical cations of tris 2,4,6-trimethylphenyl-phosphine (Mes3P+) and -arsine (Mes3As+) were studied by ESR spectroscopy. Hyperfine splitting was found to be a P = 250 gauss, a As = 279 gauss and hybridisation ratios C2 p /C2 s = 13.8 and 12.3 were established from analyses of anisotropic spectra.