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

A. V. Il′yasov Kazan Branch Academy of Sciences of the USSR Arbuzov Institute of Organic and Physical Chemistry, Kazan State University, Kazan, USSR

Yu. M. Kargin Kazan Branch Academy of Sciences of the USSR Arbuzov Institute of Organic and Physical Chemistry, Kazan State University, Kazan, USSR

E. V. Nikitin Kazan Branch Academy of Sciences of the USSR Arbuzov Institute of Organic and Physical Chemistry, Kazan State University, Kazan, USSR

A. A. Vafina Kazan Branch Academy of Sciences of the USSR Arbuzov Institute of Organic and Physical Chemistry, Kazan State University, Kazan, USSR

G. V. Romanov Kazan Branch Academy of Sciences of the USSR Arbuzov Institute of Organic and Physical Chemistry, Kazan State University, Kazan, USSR

O. V. Parakin Kazan Branch Academy of Sciences of the USSR Arbuzov Institute of Organic and Physical Chemistry, Kazan State University, Kazan, USSR

A. A. Kazakova Kazan Branch Academy of Sciences of the USSR Arbuzov Institute of Organic and Physical Chemistry, Kazan State University, Kazan, USSR

A. N. Pudovik Kazan Branch Academy of Sciences of the USSR Arbuzov Institute of Organic and Physical Chemistry, Kazan State University, Kazan, USSR

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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.

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

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

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