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3460 J . Am. Chem. SOC.

1983, 105, 3460-3463

Curve Crossing in the Cyclic Voltammetric Oxidation of
2-Phenylnorbornene. Evidence for an ECE Reaction
Pathway
Marye Anne Fox* and Ryoichi Akaba
Contribution from the Department of Chemistry, University of Texas at Austin,
Austin, Texas 78712. Received November 12, 1982

Abstract: The preparative electrooxidation of 2-phenylnorbornene (1) leads to the formation of a dienic oxidative coupling
product 2. Analysis of the anodic behavior of 1 by cyclic voltammetry indicates a novel curve crossing, the first such experimental
observation in an electrooxidation. An ECE mechanism with significant redox cross reaction is suggested as an explanation
for this unusual observation.

Introduction (i,"") depended on scan rate (v), and a plot of ip/divs. log u , ~
The recent recognition of the importance of ion radicals in a Figure 3, was characteristic of electrode processes in which
wide range of chemical transformations has prompted a reju- chemical reaction and further electron transfer follow the initial
venation of interest in characterizing the competing reaction electrooxidation.
pathways available to such intermediates. Investigations within If the applied potential is held at a value slightly negative of
our laboratory of the fate of cation radicals generated at the ip", the current continues to increase after a short (1-2 s) induction
surface of irradiated semiconductor powders' had led us to examine period. If the initial concentration of the olefin were increased,
whether intramolecular rearrangements of cation radicals might the duration of the induction period decreases and eventually
be kinetically competitive with intermolecular reactions and/or disappears. This current growth could also be seen in cyclic
deprotonation. A few cation radical rearrangements are k n ~ w n , ~ - ~ voltammograms obtained at slow scan rates, e.g., Figure 4. At
but the structural features necessary for efficient rearrangement very fast scan rates, the curve crossing disappears. Even at such
have not yet been experimentally verified. Since electrochemical rapid scan rates, the oxidative wave remains completely irre-
techniques offer a convenient and definitive method for obtaining versible.
the required data, we have examined the electrooxidative behavior On repeated scans (up to 50 cycles), a new oxidation peak
of 2-phenylnorbornene (1) by cyclic voltammetry. We describe appears that has a less positive peak potential than the starting
material (Figure 5 ) . Preparative controlled-potential electrolysis
of 1 (just positive of ip)in acetonitrile gave rise to the product
distribution shown in eq 2. Coulometric measurements obtained

\
Pi1 'Ph

here a novel curve crossing that establishes the operation of a Ph
catalytic ECE reaction pathway initiated by electrochemical 1
2
oxidation (eq 1) of this substituted olefin. This route nearly I

completely supersedes skeletal rearrangement as a fate for the 56%
electrogenerated olefinic cation radical.
Results
An unusual cyclic voltammetric curve crossing is observed when
1, at concentrations >IO-' M, is oxidized at platinum under argon
in acetonitrile or in methylene chloride containing tetrabutyl-
ammonium perchlorate (TBAP), Figure 1. Thus, an anodic scan
shows the presence of an irreversible wave at ca. +1.1 V (vs.
Ag/AgNO,: exact position depends on scan rate). On scan -310% 4 Ph
<5%
reversal, the curve does not return to the base line but rather
crosses the anodic scan, exhibiting an oxidative peak at ca. +0.9 in early stages of the electrolysis showed that one electron had
V. In the presence of small quantities of methanol or oxygen, been taken up for each molecule of 1 reacting. Although an
this curve crossing disappears and normal appearing irreversible attempted catalytic controlled-potential oxidation (at a potential
waves are observed, e.g., Figure 2. The peak current intensity one-quarter of the height of the peak potential) was too slow to
be useful synthetically, monitoring the uptake of coulombs at the
(1) Fox, M. A.; Chen, C. C. J . Am. Chem. SOC.1981, 103, 6757. oxidative peak potential showed that the rate of oxidation increases,
Greenberg, D. P.J. Chem.
(2) Jones, G.,11; Chiang, S. H.; Becker, W. G.; after a short induction period, before slowly declining as starting
SOC.,Chem. Commun. 1980, 681. Roth, H. D.; Schilling, M. L. M.;Jones, material was consumed. That the new peak can be attributed to
G.,I1 J . Am. Chem. SOC.1981, 103, 1246. the major product 2 of the electrolysis (dimer) was established
(3) Jones, G.,11; Chiang, S. H. Tetrahedron 1981, 33, 3397. by comparing its cyclic voltammogram, Figure 6, with that de-
(4) Fox, M. A.; Campbell, K. A.; Hunig, S.; Berneth, H.; Maier, G.;
Schneider, K. A.; Malsch, K. D. J . Org. Chem. 1982.47, 3408. Bock, H.; scribed above, Figure 5 . (By comparison, irreversible oxidative
Koth, B.; Maier. G. Angew. Chem., In?. Ed. Engl. 1980, 19, 2131.
(5) Rearrangements of cation radicals in the gas phase have been exten-
sively studied by mass spectroscopists. ( 6 ) Nicholson, R. S.;Shain, I. Anal. Chem. 1965, 37, 190.

0002-7863/83/ 1505-3460$01.50/0 0 1983 American Chemical Society

Chem. Chem.46 V. Am. were conducted in the presence of pyridine. incorporating the intact. J .64 mM log v 1. Chem. . except (a) scan rate = 20 mV/s.) 4 14 IO Ob V V.Phenylnorbornene J . 1961.6 500-1 V VI. implicate significant delocalization of the unpaired electron methoxylated product diminished dramatically if the electrolysis throughout the P system of conjugated olefinic radical cations. 14 lb Ob v VI.0 7 -03 Figure 1. As in Figure 1. except saturated with oxygen. 11. v.0. Dependence of the oxidative peak current intensity on scan rate.Vol. SOC. D. Cyclic voltammogram for the electrooxidation of 1 (3. chemical reactivity of unstrained. 26.I Ag/AgNO. 105. Scan rate = 200 mV/s). Ag/AgNo. The yield of the mono. T.and dimethoxylated products. that intermolecular dimerization is much faster than any of several 167. 32. Cyclic voltammogram for the electrooxidation of 1 as a function of scan rate.. Ph Ph possible intramolecular rearrangements of the radical cation 5 - 6 derived from 1. 1979. delocalized radical cations may more closely resemble that of neutral free radicals Discussion Radical Cation Rearrangement. Org. Cyclic voltammogram for the electrooxidation of 1. This result stands in sharp contrast to the rapid skeletal rearrangement of the closed-shell 2-phenylnorbornyl Analogous oxidation of 1 in methanol gave rise to a mixture c a t i ~ and n ~ ~provides ~ experimental support for calculations that of mono. No.. Steel. The isolation of a major product (7) Kleinfelter.88 and +1. As in Figure 1. Ag/AgNOj a Figure 2. 3740.under 1 atm of Ar. W. room temperature. That is. Figure 4. M. 1983 3461 14 IO 0. P. J. respectively. are observed for compounds 5 and 6. J . Aust.C. Figure 3. unrearranged norbomenyl skeleton implies (8) Coxon. CH3CN.J. R. Schleyer..Curve Crossing: Oxidation of 2. (b) scan rate = 50 V/s. Robinson. P.1 M TBAP. waves at +0. -1 5 II .. Pt.

I3-" all have been Only if there exists further electrochemical equilibration should conducted in methanol where varying distributions of stereo. Brace. Saveant.Tsutsumi.. Engl.or four-membered cases in which crossing has been reported previously have all rings is i n ~ o l v e d . ( I O ) Nelsen. of the cyclic voltammetric scan. the release of strain in three. 101. peak potential. Can. R. 323. Chem. The isolation of 2 in substantial yields in the Chem. concentration-dependent dimerization of which gives a dication Chrm. Bull. F. H .. In some. Am.. S.1975. curve crossing has occasionally been observed in polarography and Such a generalization is consistent with previous reports of in cyclic voItammetry. Chem. Am... is limited to stable (Le. Cyclic voltammogram for the electrooxidation of 2: (a) mix- Curve Crossing. Int. A. Justus Liebigs Ann. Electroanal. C . 2 would be oxidized as rapidly as (d) Nelsen. M. bg/AgNO. Lett. Y. J.. U. C. R. Proton loss from this charge-intensive species would produce L. however.100. 1968.8. 1979. Capture of the initially formed radical cation by . Saveant. H.Vol. J. M. Am. (13) Kojima. 99. SOC. ACC.. Thiebault. 38. F. (14) Inoue. SOC. J . Chem.Ob . trolyses of styrenes have been described before. H. 2117. F. J. (b) after 30 cyclic voltammetric cycles. 59. 189 . (21) Bard. The isolation of synthetically useful yields The formation of such a product (a simple ECE reaction) cannot of diene (oxidative coupling product) upon electrooxidation of 1 be responsible for the curve crossing. 105. (201 Amatore. H. H. J . S. J . S. D. The reduced yield of monomethoxylated product in the presence of pyridine is consistent with acid-catalyzed methanolysis of 1 as a prime route to the methanol adduct and with the occurrence of deprotonation as a important step at some stage of the elec- L' trooxidation. (b) authentic sample of 2. Klemm. M. Chem. The contrasting behavior observed in methanol indicates that the capture of the initially formed cation radical by methanol is more rapid than either of the pathways leading to dimerization. 1983 Fox and Akaba Scheme I. Diene Synthesis. F.- 7- . 1979. amino-substituted olefins: Fritsch..this ~ phenomenon first case of which we are aware in which such effects have been occurs relatively slowly on a cyclic voltammetric time scale and.1975. for example. furthermore. IJ Figure 5. 1978. Ed. 99.. -. Ibid. S . Cyclic voltammogram for the electrooxidation of 1. Figure 6.Chem. 10'2 ___~____ 02 Ob methanol or by oxygen is also consistent with the inhibition of V _.. H. 124. almost as to lend significant interest to processes in which it occurs. H... 1969. A reasonable scenario that can explain both the observed products and the cyclic voltammetric curve crossing is presented (9) See.and curve crossing be observed. (18) Saveant.. 107. S ... & Ph Ph Ph k- I I 12 ?/ IO 0 8 0 6 \ Ph V VI. it is clear that the electrodimerization. Electrochem. D. No. 4930.18-*' its occurrence is sufficiently rare so solution-phasc radical cation rearrangements where. Am.. 2392. Here electrooxidation leads to a radical cation. described for a catalytic oxidation. J...4367. 75. ~Although -~ conformational equilibration of involved catalytic reductions. Evans. L. F. the observed dimer 2 at a potential anodic of its own oxidative Haselbach. The continued current growth carbon radical cations like 1. Gschwind. Kessel. SOC. E. F.Jpn.. B. Am.. 1874. E. 11. Clcnnan. 13. Echegoycn. Evans. SOC. E.. Pinson.1977. M. S . Steckhan. a product that is more easily oxidized than the starting material. Steckhan. Thiebault. since scan reversal in acetonitrile is also interesting.. Ibid. K. . J. Weisman. E. 1977. Angew. (15) Engels. chemistry of 1 relates to the unusual crossing of the cyclic volt- ammetric traces for its oxidation and scan reversal. Schaefer. M. 90. F. ___. Chem. J. 1969. T. Kessel. 518. 100. P. giving localization of the odd electron is observed. Chem. D. D. a weakly nucleophilic solvent. 97. Tokumaru. Echegoyen..'* Although preparative elec. 107. is much faster than capture of the cation radical by acetonitrile. M. 661. 1979. L. Weingarten. C. ( b ) Nelsen.. 2392. curve crossing in the cyclic voltammetry of 1 (see below). SOC. Those without exception. A. N. 1965. Au-Young. a series of papers on hldrazine radical cation con- in Scheme I. (19) Amatore.. Although than that of closed shell cations. Scheme I") or through the attack of the electrogenerated cation radical on olefinic starting material (path b. Ibid. SOC. Clennan. SOC. regioisomers of the possible dimethoxylated dimers are obtained.. Sakuragi.. 1977. Chem. (a) Nelsen. 3530. A further interesting feature of the electro- ture obtained after electrolysis of I. Nelsen. ( 1 1 ) Nelsen. Ag/AgNO. L. Scheme I). J . (c) Nelsen. 1707.1977. 7. Pinson. A.. 1980. As in 2 Figure 1. it is formed. J. 204.. and our observations represent the radical ions has been extensively d e ~ c r i b e d ... J . Accordingly. 4012. Evans.'@though not a1l... should give rise to the normal trace characteristic of the product. Chem..l1radical at potentials less positive than the original oxidation peak potential ions in which conformational equilibration can be detected. J . Chem.3462 J . 1981. 97. (16) Schaefer. S. requires that a chemical reaction ensue after the oxidation. 1978. J .. J .a . J. Proposed Mechanism for Curve Crossing &-. formational equilibria. Electrwnnl. J. Buschek. E. Corrigan. C. Since the acetamides 3 and 4 are obtained in minor amounts. E. 793. (17) Dimerization of an electrogenerated cation radical has been suggested (12) Diene products have been reported in the electrooxidation of di. in the anodic dimerization of vinyl ethers: Belleau. Res. R. S . H. electrochemically reversible We interpret the curve crossing as diagnostic of a series of or nearly reversible) systems in which intermolecular reaction is chemical reactions occurring within the electrochemical time scale much less rapid than is observed for sterically accessible hydro.. K.. except (a) first scan.Ibid. Chem. 47. R. Hintz. either through collapse of two electrogenerated cation radicals (path a. A. J. G. S.:Lanyova. -. .

For 6: I-Phenylnortricyclene (6). 1495.1 M LiClO.94. than for 2'-. platinum coil counterelectrode (with a surface area more than twice that of the mesh). Cyclic voltammetry and preparative electrochem. the potential difference lacks ther. an anodic current will flow.1975. rent flow was monitored on a PAR Model 179 digital coulometer. 4. Melting still occur. G.91-2. N.47. spectrum calcd. Current-voltage 5: 1. N.and concentration-de. a as an Alfred P.6-7. 4: ' H N M R (CDCI. 75. 3.98 faraday/mol had been removed.: IIawley. J . Three crossing may be more general than has been so far recognized products were detected upon GC-MS analysis (1 50-ft capillary column. C = 229. and no further attempts at characterization were pursued. 85267-40-9. 2.27 (m. a variant on the classical Nicholson-Shain22 classification hexane/ether) led to three fractions: 2.Curve Crossing: Oxidation of 2.36 (br s.) 3418. Shain. Gas chro- 200 mV more positive than that of 2. 126. 37. pendent curve crossing in our catalytic oxidation scheme. since neither matography-mass spectroscopy (GC-MS) analysis was performed on a Finnigan Model 4023 automated GC-MS with a INCOS data system. of coupled charge-transfer chemical reactions. will be from tetramethylsilane as an internal standard. methanol before its cyclic voltammetric behavior was examined. NO. 105. each of the three products was below 2076.64 (s. Chem. D. 190. Am. Gnedin. 1 H). For preparative electrolyses.70. Chem.' . Infrared spectra (IR) disfavored because the peak potential for the oxidation of 1 is about were recorded on a Beckman Acculab 7 spectrophotometer..93 (s. catalyst to some other oxidizable couple present.4-Diphenylbutadiene (Aldrich) was recrystallized twice from curves were recorded on a Houston Instruments x-y recorder. Before electrochemistry was done. M. P.) 6 7.. 1 H). for CI5Hl9NO: of his reasoning to our catalytic oxidation (A = 1. order to the scan rates employed. Chem. Phys.) 6 7.. v. D. IR (CHCI.25. 2. (23) Hawley. Schleyer. 610.) 6 6.) until 0. Takeuchi. The theory of 36 mg.. for reversible reductions. 71. W.2030. 1 H).13 (m. The anodic and Registry No. Chem. 1450. Nonetheless. S . (26) Brown. 85267- 41-0.0 (m.. 4. "C N M R (CDCI. material..1961. etc. 97. Chem. 5 H).54 (m. determined. (27) Kleinfelter.Phenylnorbornene J . and because a more rapid reaction route ment.33-2. prepared by the procedure of Schleyer cyclic voltammograins obtained at rapid scan rates.88. B = 1+. (25) Feldberg. 125. Feldberg has shown. peak potential is reversible. Prepa- product oxidation (E) occurs and can therefore be termed an ECE rative thin-layer chromatography (neutral silica gel eluted with 50/50 reaction. 0. N o starting material remained. 142 mg. J . H . W. water. spectrometer with chemical shifts reported in parts per million downfield The catalytic oxidation of 1 by electrogenerated 2'. Am. redox equilibration can R401 liquid chromatography system on a Preppak silica column. 3: IH N M R (CDCI. S. IR (CHCI.4 (m. 1210 cm-'. High-resolution mass Conclusions. The yield of pathways of photogenerated ion radical pairs. and cur.) 2960.and 1 will Proton and carbon nuclear magnetic resonance ( N M R ) spectra were generate I+. This process will take place with an efficiency that points were obtained on a Fisher-Johns melting point block and are depends on the scan rate chosen for the cyclic voltammetry since uncorrected. 128. The most easily oxidizable partner for the necessary described here were obtained in freshly distilled acetonitrile containing redox cross reaction. High-resolution mass spectrum calcd. As the redox cross reaction freshly distilled from calcium hydride and made 0. Preparative liquid chromatography was performed with a Waters (dimerization) exists for 1+. Found: 229.1 V (vs. 1660 cm-'. Feldberg. High-resolution mass spectra were obtained with a CEC 21-1 I O instru- modynamic significance. 1. Found: 338. Feldberg. 1. partial removal of the solvent under rotary evaporation and was treated This sequence involves therefore an electrooxidation (E).20 (br s. 3 H).(E) + B-C D + A e B + C (redox cross reaction) (C) (3) (m.. All cyclic voltammograms sibilities. 5 H). 1967. Thus. in catalytic fashion.23 (s.2 M in recrystallized occurs. versibility observed in the cyclic voltammogram of an authentic and other electroactive impurities. The cell was a standard three-electrode cell with an adaptor for adding solids attached to the side. is grateful for support silver/silver nitrate reference electrode.) justifies a prediction of time. 1. 10%.4-2.29. electron exchange between 2'. a rapid with 20 mL of distilled water. a platinum coil counterelectrode. 2 H). 11. 1. (E) D e.61 (s. particularly in the prediction of reaction spectively) and a dimethoxylated product ( m / e . (22) Nicholson. this mechanism should lead to curve crossing. J . B. for C26H26: 338. The aqueous solution was extracted with chemical dimerization followed by deprotonation (C) before the ether. Chem. and the organic layer was dried over anhydrous MgSO. 83. 3 H). 31. R. 5 H).A. 232 (p)). To a preelectrolyzed so- lution of C H 3 C N / C H 3 0 H (4:l) made 0. 4. 851. R. 1600 (w). 173 potentiostat equipped with a universal programmer. Found: 227. a Dreyfus Teacher-Scholar.51. and that it may be a valuable diagnostic tool for the description 200 "C): two monomethoxylated products ( m / e 200 and 202 (p).12.20. R.05 cm?). C. The cell was equipped with a platinum Acknowledgment.) 1670 a n . The fractions containing 3 and 4 were mixtures of isomers relevant chronoamperometric details of ECE reactions complicated that could not be separated by normal or reverse-phase liquid chroma- by redox cross reactions (eq 3) have been treated in detai1. the rate-determining chemical reaction must be of comparable Preparative Electrolysis of 1 in Acetonitrile. 14 mg.1310. J . 2377. 1971. SOC.1466. Phys. 3459. an atmosphere of dry nitrogen or argon. a storage oscilloscope et was redistilled twice before its cyclic voltammetric behavior was was employed. continuing an autocatalytic cycle obtained at ambient probe temperature on a Varian E M 390 90-MHz that will generate more 2. We believe that our observation of curve Electrolysis and workup were conductzd as described above. The quasi-re. M. 1966. In particular.31 (m. and the trace will cross the LiC104. 4. 4%.55 mmol) of 2-phenylnorbornene base line at potentials positive of the oxidation potential of the The resulting solution was electrolyzed at $1. D = 2+. sistance to rearrangement of radical cations (compared with Electrolysis of 1 in Acetonitrile/Methanol. 9 H). 122.3-3. C. General Methods.23*24 tography. High-resolution mass spectrum calcd. and a the National Science Foundation. 1 H).F. and held under an atmosphere of argon was added 150 mg of 1. Phys. 1965. I. 6 H). 5. Am. Experimental Section If this same electrolysis were conducted in the presence of I R pyridine. E.1310.25 Simple extension 3310.1 M in freshly recrystallized structurally analogous carbocations) is under active investigation LiClO. The solution was concentrated by product but less positive than that of the olefinic starting material. 48. SOC. 8 H). W.. unless otherwise noted.Vol. SOC.20. re- of ion radical reactivity. the m/e 202 peak could not be derected in the GC-MS spectrum of the istry were conducted with a Princeton Applied Research (PAR) Model worked-up electrolysis mixture. Chem. especially at low conversions of starting 0. D.. 142. is 1. Anal. 36. was added 262 mg (1.4 A-B C +e- . S. 1. Ag/AgNO. 3. 70. All electrolyses were conducted under sample of 2 (in the absence of 1) negates the first of these pos.1470.' H N M R (CDCI. all solvent-electrolyte mixtures were scanned by cyclic voltammetry to ensure the absence of air. . Sloan Research Fellow and as a Camille and Henry divided cell was employed with a platinum mesh working electrode. A further elaboration of the reasons for the re. (24) Adam. for CI5Hl7NO: 227. Peters. S. To 40 mL of acetonitrile.. This research was generously supported by working electrode (0. M. 45.2034. 4237-08-5. 127. and a silver wire quasi-reference electrode. 2. 1983 3463 preparative electrolysis requires either that the radical cation of cathodic compartments were separated by glass frits and an intervening 2 be stable until workup or that it function efficiently as a redox solution of electrolyte. in our laboratory. 56%.) 6 26.97. 2: mp 153-157 OC.. IR (CHCI. J . 85267-39-6. 2329. K. that 2.