Polarographic Reduction of Iodonium Salts

Abstract

The polarographic reduction at the dropping mercury cathode of both symmetrically and unsymmetrically substituted iodonium salts is noted and reported. The mercury electrode is apparently involved in the reaction. A mechanism for the three step reduction is proposed in agreement with the experimentally found and derived polarographic data. The effect of buffering, acidity, solvent and concentration are reported in connection with the mechanism and analytical scheme for determining iodonium salts quantitatively.

Electrochemical Degradation of Aryl Sulfonium Salts

“…A solid metal electrode is used to obviate undesirable complications which might arise from the involvement of mercury in the reaction, perhaps through the aryl-mercury radicals postulated by Colichman and Maffei (15) in their reduction of diphenyliodonium ion. A solid metal electrode is used to obviate undesirable complications which might arise from the involvement of mercury in the reaction, perhaps through the aryl-mercury radicals postulated by Colichman and Maffei (15) in their reduction of diphenyliodonium ion.…”

Organic Polyvalent Iodine Compounds

“…(RC6H4)2I+BF4-+ (C6H6)3P: ^(RC,H4)P(C,Hb),+BF4-Yields of 85 (R = H), 49 (R = p-CH30), 61 (R = p-Cl), 51 (R = m-N02), and 47% (R = m-COOC2H6) (in methanol) were obtained in 6-10 hr (153a).…”

Homolytic Reduction of Onium Salts

“…Since the initial studies of Zappi and Mastropaolo, [71] the electroreduction of symmetrically substituted iodoniums salts was investigated by Colichman and Maffei, [72] then soon joined by the groups of Beringer [73] and Grimshaw. [74] No less than five different mechanisms were proposed for the reduction at a mercury cathode of diphenyliodonium cations which supported the generation of a supposed diaryliodine radical through a one-electron transfer reaction, its absorption to the electrode, and then the formation of mercurycontaining species such as the phenyl mercury radical and the diphenyl mercury, the disproportionation adduct.…”