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Electrochemical Reactions of Organic Compounds in Liquid Ammonia Subscriber access provided by University of Texas Libraries Electrochemical reactions of organic compounds in liquid ammonia. II. Nitrobenzene and nitrosobenzene Wayne H. Smith, and Allen J. Bard J. Am. Chem. Soc., 1975, 97 (18), 5203-5210• DOI: 10.1021/ja00851a030 • Publication Date (Web): 01 May 2002 Downloaded from http://pubs.acs.org on February 17, 2009 More About This Article The permalink http://dx.doi.org/10.1021/ja00851a030 provides access to: • Links to articles and content related to this article • Copyright permission to reproduce figures and/or text from this article Journal of the American Chemical Society is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 5203 ione, E,' = -0.20 VI1) may be a more favorable sensitiz- R. L. Willson, Int. J. Radiat. Biol. Relat. Stud. Phys., Chem. Med., 19, 575 (1971). er.3i The apparent limit of sensitization at the oxygen redox (14) J. D. Chaaman. J. A. Raleiah. J. Borsa. R. G. Webb. and R. Whitehouse. potential may lie in the capability of the cell to dispose of Int. J. Rabt. &I. Relat. Ski Phys., Chem. Med, 21, 475 (1972). J. D. Chapman, A. P. Reuvers, J. Borsa, and C. L. Greenstock, Radiat. 02- radicals by the superoxide dismutase enzyme and con- Res., 56, 291 (1973). sequently of other radicals which transfer electron to oxy- J. C. Asquith, M. E. Watts, K. Patei, C. E. Smithen, and G. E. Adams, gen. Radiat. Res.. 60, 108 (1974). C. L. Greenstock, J. D. Chapman, J. A. Raleigh, E. Shierman, and A. P. References and Notes Reuvers, Radiat. Res., 59, 556 (1974). L. K. Patterson and J. Liile, lnt. J. Radiat. Phys. Chem., 5, 129 (1974). (1) Supported in part by the US. Energy Research and Development Ad- K. Eiben and R. W. Fessenden, J. Phys. Chem., 75, 1188 (1971). ministration. K.-D. Asmus, A. Wigger, and A. Hengiein. Ber. Bunsenges. Phys. (2) W. M. Clark, "Oxidation-Reduction Potentials of Organic Systems", WII- Chem., 70, 862 (1966). liams and Wiikins, Baltimore, Md., 1960. G. E. Adams and R. L. Willson. J. Chem SOC.,Faraday Trans. I, 89, 719 (3) B. Eiema. J. Biol. Chem., 100, 149 (1933); B. Eiema, Red. Trav. Chlm. (1973). Pays-Bas, 50, 807 (1931); 50, 1004 (1931); 52, 569 (1933); 54, 76 C. L. Greenstock, I. Dunlop, and P. Neta. J. Phys. Chem., 77, 1187 ( 1935). (1973). (4) R. Gill and H. I. Stonehill, J. Chem. SOC., 1845 (1952). B. E. Huime, E. J. Land, and G. 0. Phillips, J. Chem Soc.. Faraday Trans. (5) M. E. Peover. J. Chem. Soc.. 4540 (1962). I, 68, 1992 (1972). (6) G. Klopman and N. Doddapaneni, J. Phys. Chem., 78, 1820 (1974). A. H. Maki and D. H. Geske, J. Am. Chem. SOC.,83, 1852 (1961). (7) I. Yamazaki and T. Ohnishi, Biochim. Blcphys. Acta, 112, 469 (1966). K. B. Patel and R. L. Willson, J. Chem. Soc., Faraday Trans. 7, 69, 814 (8) J. H. Baxendale and H. R. Hardy, Trans. Faraday Soc., 49, 1433 (1953). (1973). (9) H. Diebler, M. Eigen, and P. Matthies, Z. Naturforsch., 16, 629 (1961). P. Neta and C. L. Greenstock, Radiat. Res., 54, 35 (1973). (IO) (a) J. Lilie. G. Beck, and A. Henglein, Ber. Bunsenges. Phys. Chem., 75, D. W. Whillans, G. E. Adams, and P. Neta, Radiat. Res., 62, 407 (1975). 458 (1971); (b) M. Gratzei and A. Henglein, /bid.,77, 2 (1973). C. L. Greenstock and P. Neta, Radiat. Res., submitted for publication. (11) D. Meisei and G. Czapski, J. Phys. Chem., 79, 1503 (1975). K. Eiben and R. W. Fessenden, J. Phys. Chem., 72,3387 (1968). (12) (a) Y. Ilan, G. Czapski, and D. Meisei, Isr. J. Chem., 12, 891 (1974); (b) E. G. Janzen, Acc. Chem. Res., 2,279 (1969). submitted for publication. G. E. Adams and M. S. Cooke, ht. J. Radiat. Biol. Relat. Stud. Phys., (13) G. E. Adams, J. C. Asquith. D. L. Dewey, J. L. Foster, B. D. Michael, and Chem. Med., 15,457 (1969). Electrochemical Reactions of Organic Compounds in Liquid Ammonia. 11. Nitrobenzene and Nitrosobenzene Wayne H. Smith and Allen J. Bard* Contribution from the Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712. Received December 7, I974 Abstract: The electrochemical behavior of nitrobenzene and nitrosobenzene in anhydrous liquid ammonia was investigated by cyclic voltammetry and controlled potential coulometry. In the absence of added protonating agents, nitrosobenzene and nitrobenzene are both reversibly reduced in two one-electron transfer steps to yield the stable radical anion and stable di- anion species. In the presence of the weak acid isopropyl alcohol, the dianion of nitrosobenzene adds a single proton to form the anionic species, which can be reversibly oxidized back to parent compound. The dianion of nitrobenzene also adds a sin- gle proton and then rapidly decomposes with the loss of hydroxyl ion to neutral nitrosobenzene, which undergoes further re- duction and protonation. The overall reduction process consists of the addition of a single electron to yield a stable radical anion followed by addition of three electrons and two protons to yield the protonated dianion of nitrosobenzene. In the pres- ence of strong acid (ammonium ion), nitrosobenzene is reduced in a single two-electron reduction process to yield phenylhy- droxylamine. Nitrobenzene is reduced in two steps, involving the addition of one and three electrons, to yield the same final product, phenylhydroxylamine. Estimates of the equilibrium or rate constants for several of these reactions associated with the electrode reactions are given. The mechanism of the electrochemical reduction of nitro- graphic wave shows that the rate-determining step involves benzene to phenylhydroxylamine and aniline has received the addition of two electrons and a single prot~n.~.~The considerable attention over the past 25 years.'-I4 Most of mechanism of reduction is given as: this work involved the use of aqueous solutions containing alcohol or an ether to aid in the dissolution of the relatively C6H5N02H22*+ 2e- + H' - C,H,NOH' + H?O (slow) insoluble organic compound. Attempts at elucidating the C,H,NOH+ + 2e- + 2H' C,H,NH,OH+ (fast) reduction mechanism were made by correlating changes in - electrochemical behavior of the system with changes in pH, The reduction product of the rate-determining step which was adjusted through the use of various buffer sys- (C6HsNOH+) is reducible at a less negative potential than tems. Some studies have also been undertaken in nonaque- the starting compound (CsHsNO*H2*+), which explains ous solvent systems with addition of proton sources of vary- why this intermediate has never been detected during the ing proton-donating strength. In aqueous solution, nitroben- course of an experiment. A second wave at a more negative zene is reduced to phenylhydroxylamine in a single four- potential occurs in acid solution corresponding to reduction electron reduction step at all pH values. At pH values less of the protonated phenylhydroxylamine species than 4.7, nitrobenzene is assumed to be pre-protonated giv- CbHsNHzOH+, to yield aniline in a single two-electron ing the species C~HSNO~H~~+,while analysis of the polaro- transfer step: Smith. Bard / Nitrohenzrne and Nitrosohenzene 5204 solution, nitrosobenzene undergoes a base-catalyzed self- condensation reaction to form azoxybenzene so that the po- d larogram is found to change with time.'* In neutral and aci- dic aqueous solutions, the compound is reduced to phen- ylhydroxylarnine in a single two-electron transfer step. Bulk i electrolysis gives an overall electron addition of somewhere between one and two with the formation of azoxybenzene which was attributed to the reaction of the reduction prod- uct phenylhydroxylamine with parent compound: C,H,NO + 2e- + 2H+ - C,H,NHOH 0 t CgHSNO + CGHSNHOH ---+ C;H~--N-L;N-C~H~ + HzO In anhydrous dimethylformamide, nitrosobenzene is re- duced in a single one-electron transfer step to yield an un- stable radical anion.'' A second reduction wave correspond- ing to the reduction of azoxybenzene appears at a more neg- ative potential. In all of the solvent systems studied, nitroso- benzene is reduced at a less negative potential than nitro- benzene and, as a result, it has never been detected as an in- termediate in the reduction of nitrobenzene to phenylhy- droxylamine. The dianions of nitrosobenzene and nitroben- zene have also apparently never been prepared. Previous studies in our laboratorieslg have demonstrated the unique properties of liquid ammonia as a solvent for electrochemical investigations of organic compounds and allowed the observation of the dianion of benzophenone. This allowed the determination of reaction mechanism by Figure 1. Electrochemical cell for voltammetric and coulometric stud- the purposeful addition of protonating agents and the eluci- ies: (a) Pt wire auxiliary electrode; (b) Ag wire reference electrode in dation of individual electron transfer and protonation steps. separate compartment; (c) Au voltammetric working microelectrode; We report here an investigation of the electroreduction of (d) Pt foil coulometric working electrode; (e) silicon gum rubber sep- nitrosobenzene and nitrobenzene in anhydrous liquid am- tum for sample injection; (f) rotatable side arm for solid sample addi- monia in the absence of protonating agents and in the pres- tion. Arm and joint for attachment of cell to the vacuum line are not ence of the weak acid, isopropyl alcohol, and in the presence shown. of ammonium ion. Experimental Section C,H5NH,0H' + 2H' + 2e" ----+ C,H5NH,+ + H,O In neutral and alkaline solution, there is no evidence for Chemicals. Nitrobenzene, reaction grade quality (Matheson Coleman and Bell), was stored over molecular sieves to remove pre-protonation of the parent molecule, and polarographic traces of moisture. Nitrosobenzene (Aldrich Chemical Co.) was analysis again shows a rate-determining step consisting of considerably less pure than advertised (97%) and contained a large the addition of two electrons and a single proton.
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