Abstract
The mechanisms of redox transformations of sterically hindered [1IBQ]-[3IBQ], 9,10-iminophenanthraquinone [4IFQ], and o-aminophenol [5AP] have been studied by cyclic voltammetry. It has been shown that the reduction process in tetrahydrofuran consists of two consecutive reversible steps leading to the formation of a radical anion and a dianion. In the case of acetonitrile, only the first redox process is detected, which involves the steps of protonation and electron addition resulting in the formation of a monoanion. Quantum-chemical calculations indicate a lower degree of participation of the six-membered nonaromatic carbon ring in the spin density delocalization in the o-iminosemiquinonate radical anions as compared to o-benzosemiquinonate radical anions. The oxidation of iminoquinones results in the formation of an unstable radical cation, which undergoes further chemical transformations. An increase in the acidity of a medium leads to the formation of protonated forms with the reduction potential being shifted anodically. The introduction of screening groups makes it possible to suppress side reactions of hydrolysis and cyclization of oxidized o-aminophenol [5AP] forms. Therefore, the major product of complete electrolysis is o-iminobenzoquinone [2IBQ].
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Nevodchikov, V.I., Abakumov, G.A., Cherkasov, V.K., and Razuvaev, G.A., J. Organomet. Chem., 1981, vol. 214, p. 119.
Pierpont, C.G., Coord. Chem. Rev., 2001, vol. 216–217, p. 99.
Pierpont, C.G., Coord. Chem. Rev., 2001, vol. 219–221, p. 415.
Shults, D.A. and Bodnar, S.H., Inorg. Chem., 1999, vol. 38, p. 591.
Kahn, O., Adv. Inorg. Chem., 1995, vol. 43, p. 179.
Abakumov, G.A., Cherkasov, V.K., Nevodchikov, V.I., Kuropatov, V.A., Yee, G.T., and Pierpont, C.G., Inorg. Chem., 2001, vol. 40, p. 2434.
Sheriff, T.S., Carr, P., and Piggott, B., Inorg. Chim. Acta, 2003, vol. 348, p. 115.
Hitomi, Y., Ando, A., Matsui, H., Ita, T., Tanaka, T., Ogo, S., and Funabiki, T., Inorg. Chem., 2005, vol. 44, p. 3473.
Kaim, W., J. Chem. Soc, Dalton Trans., 2003, p. 761.
Mukherjee, S., Weyhermuller, T., Rentschler, E., Wieghardt, K., and Chaudhuri, P., Chem. Commun., 2003, p. 1828.
Mukherjee, S., Weyhermuller, T., Bothe, E., Wieghardt, K., and Chaudhuri, P., J. Chem. Soc. Dalton Trans., 2004, p. 3842.
Roginsky, V.A., Pisarenko, L.M., Bors, W., and Michel, C., J. Chem. Soc. Perkin Trans. 2, 1999, p. 871.
Roginsky, V.A. and Barsukova, T., J. Chem. Soc. Perkin Trans. 2, p. 1575
Chaudhuri, P., Verani, C.N., Bill, E., Bothe, E., Weyhermuller, T., and Wieghardt, K., J. Am. Chem. Soc., 2001, vol. 123, p. 2213.
Ward, M.D. and McCleverty, J.A., J. Chem. Soc, Dalton Trans., 2002, p. 275.
Butin, K.P., Beloglazkina, E.K., and Zyk, N.V., Usp. Khim., 2005, vol. 74, no.6, p. 585.
Chun, H., Verani, C.N., Chaudhuri, P., Bothe, E., Bill, E., Weyhermuller, T., and Wieghardt, K., Inorg. Chem., 2001, vol. 40, p. 4157.
Min, K.S., Weyhermuller, T., and Wieghardt, K., J. Chem. Soc., Dalton Trans., 2004, p. 178.
Chun, H., Bill E., Weyhermuller, T., and Wieghardt, K., Inorg. Chem., 2003, vol. 42, p. 5612.
Bill, E., Bothe, E., Chaudhuri, P., Chlopek, K., Herebian, D., Kokatam, S., Ray, K., Weyhermuller, T., Neese, F., and Wieghardt, K., Chem. Eur. J., 2005, no. 11, p. 204.
Kokatam, S., Weyhermuller, T., Bothe, E., Chaudhuri, P., and Wieghardt, K., Inorg. Chem., 2005, vol. 44, p. 3709.
Chambers, J.Q., The Chemistry of the Quinonoid Compounds, Patai, S. and Rappoport, Z., Eds., New York: Wiley, 1988, vol. 2, Chapter 12, p. 719.
Wilford, J.H., Archer, M.D., J. Electroanal. Chem., 1985, vol. 190, p. 271.
Pedersen, S.U., Christensen, T.B., Thomasen, T., and Daasbjerg, K., J. Electroanal. Chem., 1998, vol. 454, p. 123.
Okamoto, K., Ohkubo, K., Kadish, K.M., and Fukuzumi, S., J. Phys. Chem. A, 2004, vol. 108, p. 10405.
Namazian, M., J. Mol. Struct. (Theochem), 2003, vol. 664–665, p. 273.
Arai, K., Sato, T., Tamanouchi, H., Ohtomo, M., Takamura, K., Sueoka, T., and Kusu, F., Electrochim. Acta, 2000, vol. 45, p. 3029.
Abreu, F.C., Lopes, A.C., and Goulart, M.O., J. Electroanal. Chem., 2004, vol. 562, p. 53.
Magdesieva, T.V., Ivanov, P.S., Kravchuk, D.N., and Butin, K.P., Russ. J. Electrochem., 2003, vol. 39, p. 1245.
Gordon, A. and Ford, R., The Chemist’s Companion, New York: Wiley, 1972. Translated under the title Sputnik khimika, Moscow: Mir, 1976.
Organic Electrochemistry, Baizer, M.M., Ed., New York: Marcel Dekker, 1973. Translated under the title Elektrokhimiya organicheskikh soedinenii, Moscow: Mir, 1976, 731 pp.
Organicheskaya elektrokhimiya, Baizer, M.M. and Lund, H., Eds., New York: Marcel Dekker, 1983. Translated under the title Organicheskaya elektrokhimiya, Moscow: Khimiya, 1988, 1024 pp.
Toussaint, O., Lerch, K., J. Biochemistry, 1987, vol. 26, p. 8567.
Nogani, T., Hishida, T., Yamada, M., Mikawa, H., and Shirota, Y., Bull. Chem. Soc. Jpn., 1975, vol. 48, p. 3709.
Poddel’sky, A.I., Cherkasov, V.K., Fukin, G.K., Bubnov, M.P., Abakumova, L.G., and Abakumov G.A., Inorg. Chim. Acta, 2004, vol. 357, p. 3632.
Abakumov, G.A., Poddel’sky, A.I., Bubnov, M.P., Fukin, G.K., Abakumova, L.G., Ikorskii, V.N., and Cherkasov, V.K., Inorg. Chim. Acta, 2005, vol. 358, p. 3829.
Poddel’sky, A.I., Cherkasov, V.K., Bubnov, M.P., Abakumova L.G., and Abakumov, G.A., J. Organomet. Chem., 2005, vol. 690, p. 145.
Berberova, N.T., Smolyaninov, I.V., Okhlobystin, A.O., Letichevskaya, N.N., and Shinkar’, E.V., Ross. Khim. Zh., 2005, vol. XLIX, no. 5, p. 67.
Bhattacharya, S. and Pierpont, C.G., Inorg. Chem., 1992, vol. 31, p. 2020.
Harmalker, S.P. and Sawyer, D.T., J. Org. Chem., 1984, vol. 49, p. 3579.
Stallings, M.D., Morrison, M.M., and Sawyer, D.T., Inorg. Chem., 1981, vol. 20, p. 2655.
Lehmann, M.W. and Evans, D.H., J. Electroanal. Chem., 2001, vol. 500, p. 12.
Shinkar’, E.V., Okislitel’noe initsiirovanie reaktsii s uchastiem serovodoroda (Oxidative Initiation of Reactions with Participation of Hydrogen Sulfide), Cand. Sci. (Chem.), Saratov: N.G. Chernyshevskii Saratov State University, 1998, 143 pp.
Bott, A.W., Curt. Separations, 1999, vol. 18, p. 9.
Gosser, D.K., Cyclic Voltammetry: Simulation and Analysis of Reaction Mechanisms, N.Y.: VCH Publishers, 1994, 131 pp.
Budnikov, G.K., Maistrenko, V.N., and Vyaselev, M.R., Osnovy sovremennogo elektrokhimicheskogo analiza (Foundations of Modern Electrochemical Analysis), Moscow: Mir, Binom LZ, 2003, 447 pp.
Abakumov, G.A., Poddel’sky, A.I., Cherkasov, V.K., Fukin, G.K., Kurskii, Yu.A., and Abakumova, L.G., Angew. Chem. Int. Ed., 2005, vol. 44, p. 2767.
Cherkasov, V.K., Abakumov, G.A., Grunova, E.V., Poddel’sky, A.I., Fukin, G.K., Baranov, E.V., Kurskii, Yu.A., and Abakumova, L.G., Chem. Eur. J., 2006, vol. 12, p. 3916.
Bachler, V., Olbrich, G, Neese, F., and Wieghardt, K., Inorg. Chem., 2002, vol. 41, p. 4179.
Wheeler, D.E., Rodrigues, J.H., and McCusker, J.K., J. Phys. Chem. A, 1999, vol. 103, p. 4101.
Whalen, A.M., Bhattacharya, S., and Pierpont, C.G., Inorg. Chem., 1994, vol. 33, p. 347.
Heilmann, O., Hornung, F.M., Fiedler, J., and Kaim, W., J. Organometal. Chem., 1999, vol. 589, p. 2.
Kaim, W., Schwederski, B., Heilmann, O., and Hornung, F.M., Coord. Chem. Rev., 1999, vol. 182, p. 323.
Mann, Ch. and Barnes K.K., Electrochemical Reactions in Nonaqueous Systems, New York: Marcel Dekker, 1970.
Keum, S.R., Gregory, D.H., and Bruice, T.C., J. Am. Chem. Soc., 1990, vol. 112, p. 2711.
Vasconcellos, L.C., Oliveira, C.P., Castellano, E.E., Ellena, J., and Moreira, I.S., Polyhedron, 2001, vol. 20, p. 493.
Tomoda, A., Shirasava, E., Nagao, S., Minami, M., and Yoneyama, Y., Biochem. J., 1984, vol. 222, p. 755.
Simandi, L.I., Simandi, T.M., May, Z., and Besenyei, G., Coord. Chem. Rev., 2003, vol. 245, p. 85.
Simandi, T.M., May, Z., Szigyarto, I.Cs., and Simandi, L.I., J. Chem. Soc., Dalton Trans., 2005, p. 365.
Varlamov, V.T., Izv. Ross. Akad. Nauk, Ser. Khim., 2004, no. 2, p. 293 [Russ. Chem. Bull., Int. Ed., 2004, no. 2, p. 306].
Oyama, M., Higuchi, T., and Okazaki, S., J. Chem. Soc., Perkin Trans. 2, 2001, p. 1287.
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Original Russian Text © I.V. Smolyaninov, N.N. Letichevskaya, A.V. Kulakov, Ya.B. Aref’ev, K.P. Pashchenko, N.T. Berberova, 2007, published in Elektrokhimiya, 2007, Vol. 43, No. 10, pp. 1251–1264.
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Smolyaninov, I.V., Letichevskaya, N.N., Kulakov, A.V. et al. Study of the mechanism of redox transformations of sterically hindered N-aryl-o-iminoquinones. Russ J Electrochem 43, 1187–1199 (2007). https://doi.org/10.1134/S1023193507100138
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DOI: https://doi.org/10.1134/S1023193507100138