Anda di halaman 1dari 13

Journal of The Electrochemical Society, 149 共4兲 S21-S33 共2002兲 S21

0013-4651/2002/149共4兲/S21/13/$7.00 © The Electrochemical Society, Inc.

A Century of Organic Electrochemistry


Henning Lund*
Department of Chemistry, University of Aarhus, DK 8000 Aarhus C, Denmark

© 2002 The Electrochemical Society. 关DOI: 10.1149/1.1462037兴

Available electronically March 12, 2002.

The electrochemistry of organic compounds in the 20th century advantage to separate the electrochemical step which was the reoxi-
is built on the work done in the 19th century. The invention of the dation of Cr共III兲 to Cr共VI兲 from the chemical oxidation in which
battery, the ‘‘Volta pile,’’ in 1800,1 was essential for the develop- Cr共VI兲 was used to oxidize naphthalene or anthracene to the quino-
ment of electrolysis as such experiments require a current running nes. Another process in which this method was used was the bleach-
during an extended period. Volta, however, did not regard the chemi- ing of raw montan wax, and this reaction has been running commer-
cal reactions observed at the electrodes as essential for the function cially for more than 70 years by Hoechst 共now Clariant兲 on a 10,000
of the battery and his position in science was so high that no pre- ton-per-year 共t/yr兲 scale. Montan wax is extracted from lignite and
parative electrolyses were made until Faraday’s experiments in the consists of esters of long-chain acids and alcohols; after hydrolysis
eighteen thirties. Faraday was the first who made an electroorganic of the esters the alcohols are oxidized by Cr共VI兲 to the acids.
synthesis2 by electrolyzing an acetate solution and obtaining a gas- A production of sorbitol and mannitol by cathodic reduction of
eous product, ethane. The anodic oxidation of salts of fatty acids to glucose was established by Atlas Powder company10 on a 1400 t/yr
hydrocarbons with loss of carbon dioxide was developed by Kolbe3 scale, but some years later the electrolytic reaction was replaced by
to become the first useful electroorganic synthesis, and it was later high-pressure catalytic hydrogenation.
in the century extended by Brown and Walker4 to electrolysis of
salts of monoesters of dibasic acids resulting in dimerization to es- 1940-1960.—In that period electroanalytical methods, such as
ters of dibasic acids. The first electrochemical reduction of an or- polarography and voltammetry at solid electrodes, were applied to
ganic compound seems to be the reductive dehalogenation of the study of many organic molecules, and the results used for analy-
trichloromethanesulfonic acid to methanesulfonic acid5 at a zinc sis and in a few cases for guidance of electrolysis at controlled
electrode. potential. Also the use of aprotic media was begun, both for cathodic
During the second half of the 19th century preparative organic and anodic reactions.
electrochemistry bloomed and a very optimistic view on the syn- Polarography.—Polarography, current-voltage curves obtained at
thetic possibilities of the new method both for laboratory and tech- the dropping mercury electrode 共DME兲, was invented by
nical applications was expressed. In this ‘‘classical’’ period several Heyrovsky11 and was in the beginning mostly used for analysis of
oxidations and oxidative substitutions as well as reductions of nitro inorganic compounds; however, a publication on the polarography
compounds, carbonyl derivatives and dehalogenation reactions were of nitrobenzene appeared early.12 The classical photographically re-
performed; however, in most cases mixtures of products were ob-
cording ‘‘polarograph’’ was constructed by Heyrovsky and
tained. Many of these investigations were made by the groups of
Shikata.13
Elbs, Gattermann, Haber, Löb, and Tafel. Their publications ap-
Between 1925 and 1940 some organic compounds such as
peared mostly in Ber. Dtsch. Chem. Ges., Z. Elektrochemie, and J.
fructose,14 aromatic and halogenated carbonyl compounds,15
Prakt. Chem.
acetylacetone,16 and cystine17,18 were investigated by polarography.
In 1898 Haber6 published a classical paper on the stepwise re-
The two books in 1941 on polarography by Kolthoff and
duction of nitro compounds; in this he realized that by using a con-
Lingane19 and the new edition of Heyrovsky’s book20 共in German兲
stant current density the effective reduction potential would gradu-
had a great effect on polarographic research. Examples of com-
ally become more negative and that it was essential for a selective
pounds investigated polarographically in the nineteen forties are
reaction to keep the potential at the working electrode constant.
phenylsubstituted olefins and polynuclear aromatic hydrocarbons,21
However, control of the potential could only be made manually and
there was no easy way to find the optimal potential for a given aliphatic and aromatic halogen compounds,22 nitro compounds,23
reaction. diazonium salts,24 and N-heterocycles.25,26
A seminal paper by Lingane27 demonstrated that the potentials
found by polarography could be used for selective reductions at a
20th Century controlled potential at a macroelectrode, and that preparative elec-
The organic electrochemistry of the 20th century may be divided trolysis at the potential of the limiting polarographic current could
into three periods: from 1900 to 1940, from 1940 to 1960, and since establish the electrode reaction in polarography. Lingane demon-
1960. strated that 9-共2-iodophenyl兲acridine could selectively be reduced to
the 9-共2-iodophenyl兲dihydroacridine without reducing the carbon-
1900 to 1940.—The situation in the first period was not much iodine bond. The introduction of potentiostats28,29 made it easier to
different from the last decade of the 19th century with regard to perform electrochemical reactions at controlled potential.
technique, but the optimism had almost disappeared during the pe-
riod and only few publications appeared on organic electrochemistry
between 1910 and 1940. A few groups continued doing research,
mainly those of F. Fichter, S. Swann, and H. D. Law. Surveys of the
work done in that period may be found in the book by Fichter7 and
the two reviews by Swann.8
Only a few electroorganic reactions became industrial processes,
and some of the more important ones were indirect reactions where
the electrochemical step was a regeneration of an inorganic reagent.
As early as 1900 it was realized9 that in many cases it was an

In the nineteen fifties and nineteen sixties polarographic investi-


* Electrochemical Society Active Member. gations of many types of organic compounds were made and the
S22 Journal of The Electrochemical Society, 149 共4兲 S21-S33 共2002兲

results used for analysis and/or for a guidance for controlled poten- tivity of the fluoride ion is not diminished too much by solvation.
tial electrolysis, mainly reductions at a macro-mercury electrode. The preferred media are R3 N • nHF or R4 N • nHF, 42 but other
Several books were published on polarography30-34 and in Analyti- media have also been used.43 A review on electrochemical partial
cal Chemistry Wawzonek wrote a survey of polarographic publica- fluorination has recently appeared.44
tions on organic electrochemistry every second year. Later in the Another industrial production, although on a much lower scale,
century other electroanalytical techniques became more popular, al- also began operating about 1950, the anodic methoxylation of furan
though still valuable polarographic investigations were made, fore- and furan derivatives to 2,5-dihydro-2,5-dimethoxyfurans.45 Such
most by Zuman. compounds are derivatives of 1,4-dicarbonylbutene and as such are
A theory for fast polarography, oscilloscopic polarography, at a readily transformed to other compounds. A number of heterocyclic
dropping mercury electrode was developed by Matsuda compounds were prepared from 1,4-dicarbonyl-2-butenes. The reac-
and Ayabe;35 the electrode reactions were divided into reversible, tion was discontinued after some years but later reintroduced on a
quasi-reversible and irreversible according to the rate constant of the larger scale by BASF and Otsuka Chemical
heterogeneous electron transfer. The problems and their solutions
are similar to those encountered in linear sweep 共LSV兲 and cyclic
voltammetry 共CV兲.
Anodic voltammetry in aqueous or aqueous-alcoholic media is
limited by the available potential range. The use of
acetonitile/NaClO4 as medium was introduced by Lund36 in inves-
tigations on the electrochemical oxidation of alcohols and aromatic

1960-2001.—After about 1960 organic electrochemistry under-


went a rapid development. A characteristic feature of the period was
that new electroanalytical techniques made it possible to investigate
the mechanism of the electrode reactions more efficiently than pre-
viously. Another development is the introduction of indirect elec-
trolysis using organic and organometallic mediators and a growing
hydrocarbons. Preparative oxidations at controlled potential were interest of the electrochemistry of bioorganic systems. Furthermore,
made, sometimes in the presence of pyridine as base/nucleophile. new industrial applications of organic electrochemistry appeared. A
The conclusion was that the oxidation consisted of a loss of elec- few areas of the development can be mentioned here, but can only
trons from the aromatic system which then, by loss of protons or be sketchily described.
reaction with a nucleophile, formed the product共s兲. This was in con-
Electroanalytical techniques.—In the years after 1960 the further
trast to the prevailing ideas that anodic oxidations proceeded
development of electroanalytical methods made it possible to obtain
through electrolytically generated reagents, such as peroxides.
a more detailed understanding of the different steps in the electro-
Industrial processes 1940-1960.—The most important industrial chemical reactions. Both the theory for different types of reactions
application of organic electrolysis introduced in the period 1940- and the instrumentation were developed, and the introduction of
1960 was the electrochemical fluorination 共ECF兲 of organic sub- simulation of the various kinds of electroanalytical signals was a
strates, and the electrochemical manufacture of fluorinated com- great step forward.46,47 A commercially available simulation pro-
pounds has since continued to be an important industrial process. gram, Digisim, is now available.46 A monograph on the theory of the
The oldest one, the Simons ECF37 is an electrolysis of the organic electroanalytical techniques has been published,48 and discussions of
compound in anhydrous hydrogen fluoride 共aHF兲 at a nickel anode, the methods for reaction studies has recently appeared.49-51
and it results in a perfluorination of the substrate. All hydrogens in One of the most widely used techniques is cyclic voltammetry;
the compound are replaced by fluorine, double bonds are saturated, publications dealing with the influence of the rate of the heteroge-
some functional groups are retained, but a certain degradation of neous electron transfer and the rate of follow-up reactions on the
longer chains occurs. shape of the curves were published by Savéant and Vianello52 and
The mechanism of the fluorination has been discussed during the by Nicholson and Shain.53 Sometimes it is an advantage to include
years; the involvement of radical cations,38 fluoride ions, elemental the whole curve in the interpretation by calculation of the convolu-
fluorine, fluorine radicals,39 and high-valence nickel fluorides40 have tion integral which transforms the voltammogram into a
been suggested and the importance of a layer of partly fluorinated polarogram-like curve.54,55
polymers at the anode has been underlined. Recently it has been When the electron transfer is followed by a rapid follow-up re-
proposed that the fluorination goes through NiIV fluoride which in a action, a high sweep-rate is needed to outrun the reaction, and for
two-electron three-center bond共s兲 binds to the substrate. The NiIV microelectrodes of conventional diameter 共about 1 mm兲 the voltage
may be reduced in a process in which the adsorbed substrate is drop caused by the ohmic resistance is difficult to compensate elec-
oxidatively fluorinated or, alternatively, the substrate may be oxi- tronically. By the use of ultramicroelectrodes 共diam 2-10 ␮m兲 higher
dized without fluorination to give carbocations and reaction products sweep-rates may be employed.56 Using suitable ohmic-drop com-
from these or give tar; the reactive NiIV is continuously regenerated pensation it is possible to make an ohmic-drop-free electrochemical
at the anode.41 investigation in the megavolt per second range which corresponds to
The Phillips Petroleum Company has developed an electro- the development of a diffusion layer having only a few nanometers’
chemical fluorination using an electrolyte of KF•2HF with a porous thickness.57-59 However, unfortunately the ratio between the capaci-
carbon anode. The process is thought to involve electrolytic genera- tative and Faradaic current is proportional to the square root of the
tion of elemental fluorine, and the fluorination is believed to take sweep rate so at very high sweep rates the Faradaic current is just a
place within the pores of the anode. Fluorination of hydrocarbons small ‘‘bump’’ on the large capacitative current. At high sweep rates
gives partly and fully fluorinated products. The method is a useful the rate of the heterogeneous electron transfer may set a limit for the
complement to the Simon process. use of ultramicroelectrodes.
Later, other electrochemical partial fluorination reactions were Another application of ultramicroelectrodes is in the scanning
developed. In these reactions the substrate is oxidized to a radical electrochemical microscope 共SECM兲. It consists of a microelectrode
cation or cation which reacts with fluoride ion, so it is essential to 共radius 1-25 nm兲, with the distance between the tip and the substrate
perform the oxidation in a medium in which the nucleophilic reac- being piezo-controlled. At a distance between the tip and the con-
Journal of The Electrochemical Society, 149 共4兲 S21-S33 共2002兲 S23

ductive substrate similar to the radius of the tip, a molecule reduced this is the electrochemical equivalent of a Birch reduction of the
at the tip may diffuse to the substrate and be reoxidized, before it benzene nucleus.76
reacts in other ways; this gives an increase in the current as the A special medium exists in a cellular membrane where, between
apparent concentration is increased. If a fast follow-up reaction oc- the outer polar groups, there are non-polar aliphatic side chains.
curs, the changes from the expected current at different distances Important redox systems, such as ubiquinone 共UQ兲, are embedded in
give information on the rate of the follow-up reaction. The experi- the membrane; phospholipids adsorbed on mercury have been used
ments have some analogies to rotating ring-disc measurements. Us- to mimic a cellular membrane.77 Much debate has arisen on the
ing SECM the rates of fast reactions such as the dimerization of sensitivity of the electrochemical properties of UQ to the environ-
acrylonitrile in DMF60 and the rate of the oxidative dimerization of ment. The oxidation of UQH2 in a phospholipid model membrane
4-nitrophenolate61 were determined. showed a bifurcation of the electron transfer necessary to achieve an
The SECM allows the observation of the electrochemical behav- asymmetry across the membrane and to realize the required vecto-
ior of a single molecule by trapping a small volume of a dilute rial charge-transfer character.78
solution of the electroactive species, e.g., a ferrocene derivative, Organic solvents may be undesirable, especially for industrial
between the tip and the conductive substrate. An anodic current was applications, and emulsions may present an alternative. Emulsions
observed when the molecule moved in or out of the electrode- may be simple emulsions 共‘‘water in oil’’ or ‘‘oil in water’’兲 or a
substrate gap.62 ‘‘bicontinuous microemulsion.’’ 79,80 Such bicontinuous microemul-
The SECM has also been used to investigate the ‘‘reverse elec- sions are nontoxic, have a large interfacial area facilitating an inti-
tron transfer,’’ in which the electron is transferred from the reduced mate mixing of polar and nonpolar reagents, and high conductivity.
form to the oxidized in an ‘‘uphill’’ reaction. Such thermodynami- In aprotic media the choice of the anode material and anode
cally unfavored reactions are common in living systems, and the reaction is important, if an undivided cell is used; in aprotic solvents
driving force here is believed to be a proton electrochemical poten- a diaphragm is not without problems. The use of aluminum81 and
tial gradient across a membrane. A model for such a membrane is magnesium82 as sacrificial anodes solves not only the problem of
two immiscible solutions, and the role of the proton to produce a anode reaction, but the dissolved ions function as added supporting
potential drop across the interface is taken over by a supporting ion electrolyte and in many cases the magnesium ions play a special role
common to both solutions. Using ferrocyanide and 7,7,8,8- by salt formation of the product during the reaction.
tetracyanoquinodimethane 共TCNQ兲, the forward and back rate con- Electrode surfaces may be modified in many ways to get better
stants for electron transfer between water and dichloromethane have catalytic effects, chiral induction, or some other desirable effect not
been measured.63,64 obtainable at the ‘‘classical’’ electrode materials. Irreversible
A SECM may be used to probe the redox activity of individual adsorption,83 covalent attachment,84-86 and polymerization of mono-
living cells and to measure the rate of transmembrane charge trans- mers containing electroactive groups87,88 have been used. Voltam-
fer. Significant differences were detected in the redox response metric studies of the kinetics and energetics of coupled electron-
given by normal human breast ephithelial cells and metastatic breast transfer reactions in proteins adsorbed at pyrolytic graphite
cancer cells.65 Intracellular redox potentials and concentrations of electrodes have been made and it was found that the rates were more
redox components in the cell can be evaluated noninvasively.66 likely to be controlled by the chemical reactions coupled to the
Oxidative bursts of ‘‘reactive oxygen species’’ 共‘‘ROS’’兲 are used electron transfer than by the electron transfer.89 The modified elec-
by cells to fight bacteria and viruses; such oxidative bursts produced trodes are usually not stable enough for preparative reactions using
by human fibroblasts can be followed electrochemically by using a high current densities and are mostly employed as sensors;90 this
carbon fiber platinized ultramicroelectrode placed within a few mi- application will be discussed in another paper in this series.
crons of a single living cell, when the membrane is punctured with Reductive coupling reactions.—Many investigations on the mecha-
a micrometer-sized sealed pipette. In spite of experimental difficul- nism of the ‘‘hydrodimerization’’ of ‘‘activated olefins’’ were in-
ties, it has been possible to obtain electric signals indicating that the spired by the discovery by Baizer that on electrolysis under certain
oxidative bursts consist of a mixture of cytotoxic chemicals: H2 O2 , conditions, acrylonitrile, an olefin activated by an electron-
NO, ONO⫺ ⫺
2 , and NO2 . The cell survived the puncture and could withdrawing group 共EWG兲, could dimerize to adiponitrile which
perform a similar burst after a couple of hours.67 could be transformed to the two components, adipic acid and hex-
amethylenediamine, used for the synthesis of Nylon 66
Media, electrodes.—Protic solvents have continued to be used; a
newly employed solvent is 1,1,1,3,3,3-hexafluoropropan-2-ol,
CF3 CHOHCF3 . 68 The solvent has an unusually low nucleophilicity, 2 CH2 ⫽CHCN ⫹ 2 e ⫹ 2 H⫹ → NCCH2 CH2 CH2 CH2 CN
a high ionizing power and a high hydrogen bonding strength which
makes a it good solvent for cation radicals.
Although aprotic media had been employed before 1960 both for On electrolysis of an activated olefin a one-electron reduction to
reductions69 and oxidations,36 the use of such media for investiga- a dimer or a two-electron reduction with saturation of the double
tions of electrode reactions and synthesis became much more com- bond could take place, but several side-reactions, such as a Michael
mon after that date. For oxidations acetonitrile with sodium perchlo- addition of a nucleophile to the double bond or a polymerization
rate as supporting electrolyte and a Ag⫹/Ag-reference electrode was could compete with the electrochemical reactions. For the dimeriza-
first employed.36 Later methylene chloride,70 sometimes with added tion two main mechanistic possibilities presented themselves: a
trifluoroacetic acid and its anhydride to remove nucleophiles,71 was dimerization of two radical species 共RR兲 or an addition of a radical
used when acetonitrile was too nucleophilic and reacted with the species to the substrate 共RS兲 followed by an electron transfer
intermediates. Liquid sulfur dioxide offers a solvent with very low
nucleophilicity,72 but the limited solubility of supporting electrolyte
RCH⫽CH-EWG ⫹ e
共 RCH⫽CH-EWG兲 ⫺•
allows preparative electrolysis in only a few cases.73
For reductions N,N-dimethylformamide 共DMF兲, acetonitrile
共MeCN兲 and dimethylsulfoxide 共DMSO兲 have been used. Acetoni- 2 共 RCH⫽CH-EWG兲 ⫺•
共 EWGCH-CHR-CHR-CH-EWG兲 2⫺
trile is slightly more acidic than DMF and DMSO, but less likely to
lose hydrogen by atom abstraction. Acidic impurities may be re-
moved by activated aluminum oxide.74 When hydrogen atom ab- followed by product-making steps. For certain activated olefins
straction is a problem, as in SRN1 reactions, liquid ammonia can be 共e.g., some ketones兲 a preprotonation takes place in protic solution,
used.75 Methylamine with LiCl as supporting electrolyte has been so two neutral radicals dimerize. The radical-substrate dimerization
the preferred medium for reductions requiring solvated electrons; 共RS兲 may be represented by
S24 Journal of The Electrochemical Society, 149 共4兲 S21-S33 共2002兲

RCH⫽CH-EWG ⫹ e
共 RCH⫽CH-EWG兲 ⫺• formation of the d,l-form has been explained by solvation,92
complexation,96 or hydrogen bonding.97,98 Hydrogen-bonding be-
共 RCH⫽CH-EWG兲 ⫺• ⫹ RCH⫽CH-EWG tween a water molecule and the carbonyl groups of two radical

共 EWGCH-CH-CH-CH-EWG兲 ⫺• anions like a template was suggested to be essential for the predomi-
nant formation of the d,l-isomer of the dimer.97 In methanol and
共 EWGCH-CH-CH-CH-EWG兲 ⫺• ⫹ e/ 共 RR⬘ C⫽CR⬙ EWG兲 ⫺• other protic media approximately equal amounts of d,l- and meso-
forms were formed.

共 EWGCH-CH-CH-CH-EWG兲 2⫺ ⫹ RCH⫽CH-EWG
Reduction of alkyl and benzyl halides in DMF to the anions in
the presence of activated olefins may lead to a Michael addition; the
followed by product-making steps.
product anion may react in different ways, such as protonation or
The reactions are indicated to be reversible, but the degree of
reversibility depends on the competition between the backward re- SN2 reaction with the starting halide.99 In the presence of carbon
action and the further reaction. The outcome of an electrolysis is a dioxide carboxylic acids can be formed.100
function of the competition between different possible reactions and The use of sacrificial anodes such as Al101 or Mg102 may be an
thus on a number of rate constants. The progress in the elucidation advantage in the carboxylation of both aliphatic and aromatic ha-
of such reactions was therefore dependent on the development of the lides. Sacrificial anodes are also used in the carboxylation of termi-
electroanalytical techniques and simulation capabilities. The dimer- nal alkynes or diynes which on electrolysis at a silver cathode
ization of acrylonitrile was too fast for the electroanalytical tech- formed dihydrogen and the substrate anion that reacted with the
niques in the sixties and seventies, so other compounds with slower carbon dioxide.103
kinetics were used for studying electrohydrodimerizations, not only Carboxylation may be catalyzed by nickel complexed with
of activated olefins, but also other types of compounds, e.g., an- Ph3 P104 or salen;105 electrolysis of unsaturated haloaryl ethers at a
thracenes substituted with EWG, which could dimerize reductively. carbon fiber cathode in DMF in the presence of NiII (cyclam) leads
An early argument against R-R dimerization was that two radical to dihydrobenzofuran or dihydrobenzopyran derivatives in a tandem
anions could not dimerize due to electrostatic repulsion, but using cyclization-carboxylation.106
different electroanalytical techniques and setting up working curves
for the expected theoretical behavior Bard,91 and Savéant92 could
show that the more slowly reacting 1,2-diactivated olefins in aprotic
medium dimerized reductively through a coupling between two radi-
cal anions.
However, the elucidation of a reaction mechanism for some ac-
tivated olefins was made difficult by its dependence on the medium,
as this could influence the rate constants of the competing reactions Another type of reductive coupling is intramolecular coupling;
differently. An illustrative example is the hydrodimerization of an the ring closure may result from a reaction between an electrochemi-
alkyl cinnamate in superdry DMF, in DMF containing a small con- cally generated nucleophile and an electrophilic center or by a radi-
centration of water, and in methanol. In superdry DMF the protona-
cal coupling.
tion of the dimerized dianion is not fast compared to the dissociation
of the dianion, whereas a small water concentration is enough to Reduction in acetonitrile/Et4 NOTs with diethyl malonate as pro-
ensure a fast protonation of the dianion and thus effectively an irre- ton donor of an activated olefin having a carbonyl or cyano group in
versible dimerization.93 In methanol a preprotonation may take an ortho position results in a ring closure by attack of the nucleo-
place and the dimerization occurs between two neutral radicals. If philic ␤-carbon on the carbonyl group.107 A similar reductive ring
the reversibility of the dimerization in the superdry medium is not closure where the ␤-carbon attacked a halide had been described
taken into account, the interpretation of the electroanalytical data earlier.108 A slightly different type of ring closure takes place when
may lead to a false mechanism. a carbonyl derivative with an unactivated double bond in the ␦- or
The discussion of the correct interpretation of experimental data ␧-position is reduced with constant current in an undivided cell us-
obtained by different research groups on the R-R vs. R-S problem ing about 10 F/mol. In this case, however, it is the carbonyl radical
was in the beginning of the eighties rather heated. Since then further anion 共or the oxygen-protonated radical anion兲 which adds to the
development of instrumentation and power of simulation of theoret- double bond.109
ical curves have indicated that in general the hydrodimerization of The reductive formation of nucleophiles followed by an attack
activated alkenes proceeds through a radical anion-radical anion on an electrophilic center is also the basis for the synthesis of many
coupling.94,95 heterocyclic compounds.110-112 Thus the reduction of the nitro group
It was also early recognized that addition of a small concentra- in suitable ortho-substituted nitro compounds to the hydroxylamine
tion of water to the stage may lead to an N-oxide of an N-heterocyclic compopund;
thus, for example, o-nitrobenzalacetylacetone is reduced to
3-acetyl-2-methylquinoline-N-oxide.110

aprotic medium increased the rate of the dimerization, but there was
discussion of the role of the water. In such media activated olefins, On reduction of aryl halides the initially formed radical anion
such as derivatives of cinnamic acid 共esters, amides, nitriles兲, have decomposes to halide ion and the aryl radical; the aryl radical is
been found to hydrodimerize nearly exclusively to the d,l-form; the generally more easily reduced than the substrate or it may abstract a
esters made a ring closure to an all trans ring. The predominant hydrogen atom from the solvent system, but in suitably substituted
Journal of The Electrochemical Society, 149 共4兲 S21-S33 共2002兲 S25

compounds the radical may attack a phenyl ring with ring closure. product are formed, but by having a great excess of the cheaper
Thus, for example, 5-共2-chlorophenyl兲-1-phenylpyrazole is reduced carboxylate good yields of the cross-coupled product may be ob-
to pyrazolo关1,5-f兴phen-anthridine.113 tained; such a reaction has been employed for the synthesis of
pheromones.124 The cross-coupled Kolbe reaction has been com-
Anodic substitution and coupling.—Anodic reactions without added pared with low temperature photolysis of neat unsymmetrical diacyl
mediator may involve a loss of electrons from the substrate or from peroxides, and the latter was found to be better with regard to yield
the solvent The previously mentioned pyridination of anthracene36 and selectivity.125
and the methoxylation of furan45 are examples of the first type; in Radicals produced in the Kolbe raction may also add to olefins,
some oxidations the solvent is oxidized with loss of an electron and and the radical thus formed can dimerize or be oxidized to a carbe-
a proton and the radical thus formed abstracts a hydrogen atom from nium ion which can react with a nucleophile or may lose a proton to
the substrate.114,115 an alkene. This type of addition of a radical to an alkene has been
Methoxylation of alkylbenzenes may take place in the side chain used in ring-closure reactions126 and to introduce a trifluormethyl
or in the nucleus; 4-methylanisole can thus form methoxybenzyl group in different compounds.127,128
methyl ether or 1,1,4-trimethoxy-4-methylcyclohexa-2,5-diene de-
pending on the medium; when the electrolysis is conducted under
conditions where formation of methoxy radicals also takes place,
nuclear methoxylation dominates.116 The methoxylation of methyl-
benzenes is of industrial importance; BASF oxidizes substituted
toluenes in methanolic solution at a carbon anode in a capillary-gap
cell to the substituted benzaldehyde dimethylacetal.
RC6 H4 CH3 ⫺ 4 e ⫹ 2 CH3 OH → RC6 H4 CH共 OCH3 兲 2 ⫹ 4 H⫹

Another useful reaction is the methoxylation of


N,N-dialkylamides, the first example being the oxidation of dim-
ethylamides in MeOH/NH4 NO3 to N-alkoxy-N-methylamides; un- The further oxidation of the radicals to carbenium ions can lead
der these conditions an oxidation of both the amide and the nitrate to acetoxylation, methoxylation or acetamidation, depending on the
ion takes place.117 A large number of heterocyclic derivatives have solvent. The methoxylation reaction has been used in several syn-
been prepared through the anodic methoxylation of acylated theses, e.g., of carbohydrate derivatives129 or oligopeptides.130
heterocycles,118 in peptidomimetics,119 and in the first example of Anodic oxidation of 2,4,6-tri-t-butylphenolate gives stable radi-
combinatorial electrochemistry.120 cals, whereas 2,6-di-t-butylphenolates substituted in the 4-position
with a primary alkyl group dimerize reversibly to a para-substituted
quinol ether on anodic oxidation. In CV an irreversible peak is ob-
served at fast sweep rates, whereas at slower sweep rates a cathodic
peak due to the reduction of the radical appears. This cathodic peak
becomes larger when the sweep rate is decreased due to the in-
creased influence of the reversibility of the dimerization.131

Oxidation of aromatic compounds in acetic acid with some acetic


anhydride may result in acetoxylation; similar to the methoxylation,
attack on alkylarenes may occur both in the nucleus or in the side
chain. Substitution in the aromatic ring requires the presence of
acetate ion.120 When acetonitrile containing some trifluoracetic an-
hydride is the solvent, the carbocation formed by oxidation may
attack the solvent in a Ritter-type reaction; methylsubstituted ben- Indirect electrolysis.—In indirect electrolysis the electrons are not
zenes are good substrates for such an acetamidation.121 Even exchanged heterogeneously directly between the electrode and the
n-alkanes may be oxidized in MeCN/R4 NBF4 with acetamidation at substrate, but the electrode exchanges electrons with a compound, a
a secondary carbon.122

Ar-CH3 ⫺ e
Ar-CH⫹• ⫹ ⫹ ⫹
3 共 ⫺H 兲 → ArCH2 (⫺e) → ArCH2 共 ⫹MeCN 兲 → ArCH2 -N⫽C -Me共 ⫹H2 O 兲 → ArCH2 NHCOMe ⫹ H
• ⫹

The Kolbe reaction was the first useful electroorganic synthesis mediator, which then in the solution exchanges electrons with the
and it is still under active investigation. In the classical Kolbe reac- substrate. A theory of the dependence of the rate of electron transfer
tion the carboxylate is oxidized to a radical, but under certain con- on the driving force for outer-sphere electron transfer was developed
ditions this radical may be oxidized further to a carbenium ion in the by Marcus132 for inorganic systems; later it was shown to be appli-
so-called non-Kolbe reaction. The influence of solvent, current den- cable also for organic compounds.133,134 The Marcus equation gives
sity, degree of neutralization and chain length on the selectivity of the free energy of activation as a quadratic dependence on the driv-
the Kolbe vs. the non-Kolbe reaction has been clarified.123 ing force and the reorganization energy, the latter being the sum of
RCOO⫺ ⫺ e → R• ⫹ CO2 → 1/2 R-R ⫹ CO2 the solvent and structural reorganization energy necessary to reach
the transition state for the electron transfer. For relative small driv-
R• ⫺ e → R⫹共 ⫹Nu⫺兲 → R-Nu ing forces the rate of electron transfer increases with increasing
driving force, but when the driving force exceeds a certain value the
A useful extension of the classical reaction is the Kolbe cross- quadratic dependence in the Marcus equation leads to the counter
coupling reaction in which two carboxylates are oxidized simulta- intuitive result that a further increase in driving force results in a
neously. Both the two symmetrical dimers and the cross-coupled decrease in the rate of electron transfer. For several years attempts to
S26 Journal of The Electrochemical Society, 149 共4兲 S21-S33 共2002兲

experimentally verify this predicted result failed, but eventually it A ⫹ e


A⫺•
was shown that experiments supported the theory.135,136 In the first
experiments the rate was measured of the electron transfer from a ArSO2 -CH共 R兲 -C共 R⬘ 兲 ⫽CH-CH2 -CH2 -SO2 Ar ⫹ 2 A⫺• ⫹ 共 H⫹兲
biphenyl radical anion bound to one end of a steroid structure to an
aromatic compound A bound to the other end of the structure. → ArSO⫺
2 ⫹ RCH2 C共 R⬘ 兲 ⫽CH-CH2 -CH2 -SO2 Ar ⫹ 2 A

Macrocyclic nickel complexes have been used as catalysts in the


activation of organic halides. Electrogenerated Ni共I兲-complexes re-
act rapidly with alkyl bromides and iodides, the reaction leads to
alkyl radicals and regeneration of the Ni共II兲-complex. In most cases
electrolysis of alkyl halides in the presence of catalytic quantities of
nickel complex leads to the complete reduction of the alkyl
Indirect electrolysis can be a simple redox catalysis or it can
halide.145
involve a chemical catalysis;137 in redox catalysis the mediator acts
Recently nanometer-sized monolayer-protected clusters on gold
merely as an electron donor or acceptor whereas an adduct between
共MPCs兲 have been used in indirect electrolysis.146 MPCs are pre-
the donor and acceptor which decomposes in a further reaction is
involved in chemical catalysis. pared by reducing a gold salt (AuCl⫺ 4 ) in a two-phase system in the
Inorganic mediators have been employed during the whole cen- presence of an alkanethiol by NaBH4 ; gold particles of 1-3 nm
tury, but the use of organic compounds as mediators began in the diameter bearing a surface coating of thiol are obtained. These par-
middle of the seventies.138-141 Typically an aromatic compound is ticles are stable and can repeatedly be isolated by filtration from and
reduced in an aprotic medium to the radical anion or dianion which redissolved in organic solvents.147 MPCs may be prepared with
transfers an electron to a substrate. On electron uptake the substrate functional groups in the ␻-position via a place-exchange reaction in
forms a radical ion which undergo a fast, irreversible reaction, usu- which the original alkanethiol is replaced by a thiol bearing the
ally a cleavage, or it reacts by a dissociative electron transfer to a required groups.148 Using anthraquinone bound to such monolayer-
radical and an anion. For an aromatic substrate the aryl radical is protected gold clusters, each bearing about 18 anthraquinone units,
usually reduced by the mediator to the anion, whereas the radical indirect reduction of 1,1-dinitrocyclohexane was accomplished. The
from an aliphatic substrate has a possibility of being reduced by or catalytic efficiency of the clusters, the ratio between the current in
couple with the mediator. For an aromatic mediator, A, and an ali- the presence of the substrate and the current of the mediator alone
phatic halide, RX, the reactions can be described in a simplified way divided by the concentration of the substrate, was found to be higher
as than that of monomer anthraquinone which was attributed to the
smaller diffusion coefficient of cluster-bound anthraquinone relative
A ⫹ e
A⫺• to that of monomer anthraquinone; this resulted in a spatial com-
pression of the reaction zone next to the electrode. A review on
A⫺• ⫹ RX → A ⫹ R• ⫹ X⫺ MPCs has been published.149
kc Self-assembled monolayers 共SAMs兲 of alkylthiolates on gold
A⫺• ⫹ R• ——→ AR⫺ may also be used for immobilization of enzymes on an electrode;
this may avoid a partial denaturation of the enzyme often encoun-
kc tered with direct adsorption and still establish a short distance be-
A⫺• ⫹ R• ——→ A ⫹ R⫺ tween the prosthetic group and the electrode surface. This approach
has been used in biosensors.150
The coupling reaction has been used for the synthesis of several Even living cells use the advantage of indirect electrolysis; ex-
compounds,142,143 and the competition between coupling and reduc- tracellular electron transfer may be a general mechanism whereby
tion has been used, as described below, to estimate the potentials of microorganisms generate energy for cell growth and/or
short-lived radicals. maintenance.151 Although mostly used for reducing metal salts, es-
pecially iron salts, reduction of organic compounds is also found, for
instance reduction of carbon tetrachloride.152
Indirect electrochemical oxidation using inorganic salts has been
used during the whole century, but more recently the use of organic
mediators has been employed. Anodic oxidation in acetonitrile or
dichloromethane of brominated derivatives of triphenylamine forms
a stable radical cation which may oxidize substrates such as thioet-
hers. It thus selectively cleaves the methoxybenzylthio group in the
presence of other protecting groups such as trityl or tert-
butyloxycarbonyl 共BOC兲.153 Other compounds such as polysubsti-
Redox catalysis is in most cases based on the fact that the rate tuted biphenyls or dibenzothiophenes may also be used as mediators
constant for the heterogeneous electron transfer to nonconjugated in anodic indirect reactions.154
compounds is low due to the comparatively large changes in solva-
tion energy and in bond-length and bond-angles associated with the
electron uptake and bond cleavage. An advantage of indirect elec-
trolysis is that the reduction can take place at a potential less nega-
tive than that necessary for a direct reduction. The reduced mediator
diffuses into the bulk of the solution and the reaction with the sub-
strate is then a homogeneous reduction; the indirect electrolysis can
thus be compared to a reduction taking place at a three-dimensional
electrode. The radicals which are formed in the solution by the elec- Some information on the electron exchange of redox enzymes
tron transfer might add to alkenes or other unsaturated groups.143 may be gained using CV of immobilized enzymes; such an immo-
Another advantage of redox catalysis is that very selective cleavage bilization should avoid adsorptive denaturation and improper orien-
and deprotection reactions may be performed. An example is the tation of the enzyme. One way is to use an antibody-antigen binding
cleavage of an allyl phenyl sulfone without cleavage of a homoallyl procedure155 by which the full activity of the enzyme is preserved
phenyl sulfone in the same molecule144 and a long life-time achieved. The homogeneous enzymatic catalysis
Journal of The Electrochemical Society, 149 共4兲 S21-S33 共2002兲 S27

of the oxidation of glucose to glucono-␦-lactone by glucose oxidase form stable radical anions are chosen as electron donors. The radical
has been investigated by CV using ferrocenium methanol as media- anion (A⫺. ) transfers an electron to the substrate, typically an alkyl
tor. The ferrocenium oxidizes FADH2 to FAD 共flavin adenine di- halide 共RX兲, which then dissociates to the alkyl radical and halide
nucleotide兲 and FAD oxidizes glucose. From the catalytic increase ion. The competition reactions are:
in CV of the immobilized enzyme in the absence and presence of kc
glucose information on the kinetics of the reactions can be
A ⫺• ⫹ R • ——→ AR ⫺
gained.156 A similar investigation with ferrocene attached at the end
of a long chain through an antibody to the supramolecular structure ke
mimicing a co-enzyme has been made.157 A ⫺• ⫹ R • ——→ A ⫹ R ⫺
Radicals.—In the second half of the 20th century radical chemistry
has been of steadily increasing importance. The redox potentials of The competition is expressed by a competition parameter q
the radicals may help in predicting the course of such reactions. For ⫽ k e /(k e ⫹ k c ); for q ⫽ 0 the coupling dominates and for q close
relatively long-lived radicals, conventional CV can measure the to 1 the reduction of R . to R ⫺ takes place. q-values for different
thermodynamic potentials, but for short-lived radicals the rate of the radical anions are measured and a plot of q vs. E Ao gives an S-shaped
follow-up reaction and the rate of the heterogeneous electron trans- curve. From the potential of the midpoint of the S-shaped curve,
q
fer influence the measured potentials. At fast sweep-rates the E 1/2 , the standard potential, E Ro , can be calculated when the total
iR-drop becomes inconveniently large. For aliphatic radicals slow self-exchange reorganization energy ␭ R is known or estimated. k c is
electron transfer may shift the peak potential about 1 V from the assumed constant164,165 and about 109 M⫺1 s⫺1 . The weak point of
standard potential of the radical.158 A review of the measurement the method is the estimation of ␭, but the method gives a reasonable
and estimation of redox potentials of organic radicals has been potential determination of short-lived radicals using easily available
published.159 apparatus.
The introduction of ultramicroelectrodes54 in the nineteen eight-
ies made it possible to outrun the follow-up reactions in many cases Electrogenerated bases.—When electrons are added to a molecule,
and obtain the standard potentials as the midpoint between the ca- the resulting species may be characterized as a nucleophile, a base
thodic and anodic signal. The distance between two potentials may and/or an electron donor depending on the follow-up reaction共s兲. In
be larger than for a reversible reaction due to a slow electron trans- most earlier reactions the anion/base generated during an electrolytic
fer, but the rates of the forward and backward reaction are usually reduction was protonated by the solvent system or an added proton
comparable. donor, so in protic solvents electrogenerated bases 共EGB兲 were not a
Radicals may be formed by photolysis and detected by voltam- problem. The first published reaction in which it was observed that
metry; a sensitive method of voltammetric detection was developed the EGB played a role in the reaction scheme was the reduction of
by Wayner et al.160 The principle is that the intensity of the light, cyanoethylphosphonium toluenesulfonate in aprotic medium.
and thus the concentration of the radicals formed, is modulated by a Baizer166 realized that the electron consumption n ⫽ 1 observed in
mechanical chopper which blocks the light with a certain frequency. the controlled potential reduction of the phosphonium salt in dry
Phase-sensitive detection of the voltammetric signals from the radi- DMF was caused by the deprotonation of the substrate by the anion
cals filters off noise and other signals not in phase with the chopper. formed in the reduction, and that the anion of the substrate was not
By this means radicals may be detected in the 10⫺7 molar range reducible at the applied potential. Half of the substrate was thus not
where second order follow-up reactions become less important. Of- reduced, but survived the reduction as the non-reducible anion. A
ten both the reduction and oxidation potentials of the radical can be kinetic analysis of the self-protonation reaction 共a ‘‘father-son reac-
obtained tion’’兲 has been published by Savéant and Vianello.167
The first example of a synthetic application of an electrogener-
h␯ ated base using the type of compounds which later were called ‘‘pro-
R-CO-R → 2 R• ⫹ CO bases’’ was provided by Lund.168 The strategy was to reduce a com-
pound more easily reducible than the substrate components, so the
h␯ only function of the reduced probase was to abstract a proton from
t-Bu-O-O-t-Bu → 2 t-BU-O• one of the reaction partners. Azobenzene was reduced in a DMF
solution in which also benzaldehyde and benzyltriphenylphospho-
t-Bu-O• ⫹ RH → t-Bu-OH ⫹ R• nium chloride were dissolved. In this solution azobenzene was the
most easily reduced species and the EGB formed 共the radical anion
Another way of measuring potentials of short-lived radicals is by of azobenzene and/or the monoanion of hydrazobenzene兲 deproto-
photoelectron injection which was developed by Russian nated the phosphonium salt, and the ylid thus formed reacted with
scientists.161 A metal electrode is illuminated with a short laser pulse benzaldehyde in a Wittig reaction to form stilbene
and low-energy electrons are injected into the solution and are sol-
vated close to the electrode 共10-60 Å兲. Most of the electrons diffuse PhN⫽NPh ⫹ e
PhN⫽NPh⫺•
back to the electrode, but some may react with the substrate to form PhN⫽NPh⫺• ⫹ Ph3 P ⫹ CH2 Ph
radicals. Depending on the potential of the electrode the radicals
may or may not be reduced at the electrode, which influences the net → PhNH-N• -Ph ⫹ Ph3 P⫹-CH⫺-Ph
photoinduced charge. By doing a series of experiments at different
electrode potentials a kind of current-potential curve may be ob- Ph P⫹-CH⫺-Ph ⫹ PhCHO → Ph3 PO ⫹ PhCH⫽CHPh
tained from which the reduction potential of the radical can be
found. As the radicals have a very short distance to diffuse to the In DMF and DMSO rather strong EGBs can be made and these
electrode even potentials of short-lived radicals may be obtained. bases may be so strong that they may replace conventional strong
Several types of radicals have been investigated by this bases such as BuLi, which have certain disadvantages for industrial
method.161,162 use. By using sterically hindered bases the nucleophilic reactions of
Indirect electrolysis of alkyl halides was discussed above and the EGB may be suppressed.169
these reactions were further developed by the Aarhus group to a An attractive way to produce an EGB is to reduce a compound
method for determination of potentials of short-lived radicals.163 with a slightly acidic hydrogen at an electrode with a low hydrogen
The method is based on the competition between coupling of a overvoltage. This has been exploited by Shono170 who by direct
radical anion with a radical and reduction of the radical by the electrolysis of 2-pyrrolidone 共pKA (DMSO) ⫽ 24.2兲 in DMF at a
radical anion. Aromatic compounds which in an aprotic medium platinum electrode formed the anion. As the hydrogen evolution
S28 Journal of The Electrochemical Society, 149 共4兲 S21-S33 共2002兲

requires a rather negative cathode potential, the base had in most sical SN1 and SN2 reactions 共or hybrids between them兲. In the in-
cases to be formed before the addition of the substrate. vestigation of a possible electron transfer mechanism in the
Carbon bases may be formed by reduction of a halogen com- substitution, the Aarhus group used a nucleophile, the anion of 1,4-
pound. An example of this is the reduction of a low concentration of dihydro-4-methoxycarbonyl-1-methylpyridine, which on electro-
carbon tetrachloride in the presence of benzaldehyde and a high chemical oxidation gave a stable radical, so the reversible oxidation
concentration of chloroform. The carbanion formed on reduction of potential of the nucleophile could be found by CV. Other similar
carbon tetrachloride adds to benzaldehyde and the adduct deproto- nucleophiles were also used. The method consisted in a comparison
nates chloroform to the reactive carbanion171 of the rate of reaction of the nucleophile with an alkyl halide with
the rate of electron transfer from a stable radical anion with the same
CCl4 ⫹ 2 e → CCl⫺
3 ⫹ Cl

oxidation potential as the nucleophile to the same alkyl halide. For
RCHO ⫹ CCl⫺ ⫺
3 → RCH共 O 兲 CCl3
sterically hindered alkyl halides the two rates were practically the
same, indicating that in this aliphatic nucleophilic substitution the
RCH共 O⫺兲 CCl3 ⫹ HCCl3 → RCH共 OH兲 CCl3 ⫹ CCl⫺
3
rate of the transfer of a single electron from the nucleophile to the
alkyl halide was the rate-determining step.180,181 In less sterically
Dioxygen is reduced to superoxide anion which is a relatively hindered alkyl halides the rate of substitution was faster than the
weak base, but on protonation two superoxide anions can form the expected rate of electron transfer indicating either a competition
stronger base HO⫺ 2 .
172
Dioxygen may be used as EGB,173 but the between electron transfer and SN2 or a kind of hybrid between the
substrate anion is likely to react with dioxygen to a peroxide. This two mechanisms.
has been avoided by using a low concentration of oxygen in a depro-
tonation of nitromethane which was used in a condensation of ni-
tromethane with aldehydes. By having nitromethane as solvent, the
competition between deprotonation and reaction with dioxygen fa-
vored the deprotonation.174 An alternative reaction of superoxide
anion has been suggested in the reduction of oxygen in the presence
of 4-nitrotoluene; the superoxide anion abstracts a hydrogen atom
from the methyl group and the benzylic radical is oxidized by
dioxygen.175 Chiral induction.—Several different ways have been explored for
Aromatic nucleophilic substitution.—The radical chain nucleophilic the transfer of chirality during electrochemical reactions. Horner182
used chiral supporting electrolytes, but obtained rather modest chiral
substitution, SRN1, discovered by Kornblum, Russell and Bunnett,
has been investigated by Savéant et al.176 by electrochemical tech- induction. Seebach183 used a chiral solvent, S,S(⫹)2,3-
niques. The reaction involves the following steps where AX is an dimethoxy-1,4-bis(dimethylamino)butane, with no better result.
aromatic compound substituted with a leaving group X and Nu⫺ is a Grimshaw184 employed alkaloids adsorbed at the electrode as chiral
‘‘soft’’ 共i.e., easily oxidizable兲 nucleophile proton donors, but the enantiomeric excess (ee) was not above 20
%. Other groups have attempted to improve the induction185-188 us-
ArX ⫹ e
ArX⫺• ing adsorbed alkaloids and fairly high induction has been obtained
in some cases.
ArX⫺•
Ar. ⫹ X⫺ Chemically modified electrodes have been used to introduce
chirality. Miller189 modified the cathode with (S)-phenylglycine and
Ar• ⫹ Nu⫺
ArNu⫺•
obtained a modest ee in the reduction of prochiral ketones.
ArNu⫺• ⫹ ArX
ArNu ⫹ ArX⫺• Nonaka190 prepared different electrodes coated with optically active
poly共aminoacids兲 and got variable and sometimes very high ee both
The cathodic reduction of the radical or a hydrogen abstraction in reductions and oxidations, and Osa191 used an anode modified
from the solvent are terminating reactions. Liquid ammonia has with TEMPO in the presence of (⫺)-sparteine in an oxidative cou-
mostly been used as a solvent to minimize hydrogen abstraction pling.
from the solvent by the aryl radical. An attractive way to obtain stereoselective reactions would be to
Aromatic radical anions (ArX⫺. ) have a certain lifetime that use enzymatic reactions in which the active form of the enzyme was
gives them time to diffuse from the electrode and thus avoid reduc- regenerated electrochemically. Enzymes, like most proteins, ex-
tion of the relatively easily reducible radical. In some cases an in- change electrons slowly with an electrode, so to get a useful syn-
direct reduction of ArX may be an advantage.177,178 The cleavage of thetic route this difficulty must be overcome. Another problem
the substrate radical anion to an aryl radical and a nucleophile X⫺ is might be to obtain long-time stability of the enzyme necessary for
the opposite reaction of the coupling of the nucleophile, Nu⫺, with preparative applications. Different approaches to solve these prob-
the aryl radical. Differences in nucleophilicity and concentration de- lems have been published.
termine the course of the reaction. A redox-enzyme usually requires a co-factor and in most cases a
Aliphatic halides undergo as a rule not an electrochemically in- mediator is necessary to ensure a fast exchange of electrons between
duced SRN1 reaction, as the radical is formed close to the electrode the electrode and the co-factor. One approach has been to immobi-
in a dissociative electron transfer and is thus reduced to the anion lize the enzyme, its co-factor, and a mediator at a poly共acrylic acid兲-
before it can react with the nucleophile. An interesting case of a coated graphite-felt electrode. The effective surface area is rather
benzylic halide is the classical reaction between 4-nitrocumyl chlo- small and the reactions are not fast so the productivity is limited by
ride and 2-nitropropanate ion which reacts in a chain reaction with- slow reaction steps and not by mass transport.192
A way to increase the effective surface area is to deposit a fibrous
out external stimulation in a ‘‘thermal’’ SRN1 reaction. Savéant179
layer of poly共aniline兲 on reticulated vitreous carbon and adsorb the
showed that an outer-sphere electron transfer from the anion to the
enzyme on the poly共aniline兲. The enzyme was stabilized by cross-
substrate was thermodynamically unfavored, but that a decrease in
linking with glutaraldehyde and then immobilized with a thin layer
driving force was able to change the mechanism of the reductive
of poly共1,2-diaminobenzene兲. By this increase in the effective sur-
cleavage of the substrate from a stepwise to a concerted reaction.
face layer the current density could, for a not too high substrate
Aliphatic nucleophilic substitution.—Indirect electrolysis has been concentration, have some dependence on the mass transport rate,
used to investigate the mechanism of the aliphatic nucleophilic sub- and the cross-linking of the enzyme with glutaraldehyde increased
stitution which traditionally has been regarded as following the clas- considerably the stability of the enzyme.193
Journal of The Electrochemical Society, 149 共4兲 S21-S33 共2002兲 S29

A further possibility is to use an ultrafiltration membrane with a Besides applied research for the development of batteries, re-
molecular weight cutoff so that the enzyme cannot penetrate it. This search on conducting polymers for electrochromic displays 共ECD兲
approach requires that a redox catalyst and the co-factor be bound to has been continuing. An ECD is based on an electrochemical reac-
a soluble polymer such as polyethylene glycol. This procedure has tion of a material that displays a visual change on changing its redox
been called ‘‘homogeneous immobilization’’ by Steckhan,194,195 and state, such as for instance, polypyrrole209 and polyaniline.210 By
it avoids the diffusional limitations at the electrodes with immobi- using polyaniline with poly-o-phenylenediamine and polymetanilic
lized enzymes. In the enzyme membrane reactor the product diffuses acid, the three primary colors could be developed.211,212
through the membrane, whereas the enzyme, the mediator and the Another type of conducting polymer is DNA; electron vacancies
co-factor, all bound to polyethylene glycol which cannot diffuse 共holes兲 formed by oxidants such as hydroxyl radicals or singlet oxy-
through the membrane, are recirculated. The reaction is controlled gen may, in spite of the catalase that is present, attack DNA; such
by proper adjustment of the residence time in the reactor. This ap- oxidative damage may contribute to ageing of cells, mutagenesis,
proach might be the best route for development of electroenzymatic and cancer. Holes may, however, be transferred across up to 50 base
processes for industrial use. pairs in a DNA duplex in homogeneous solution by hopping be-
tween cytosine-guanine 共CG兲 base pairs213 to a remote G which is
Polymers.—Electrogenerated nucleophiles/anions have been shown oxidized.214-217 When not aligned in parallel, condensed-phase DNA
to initiate polymerization of suitable monomers; in the absence of duplexes are electrically insulating, but when aligned their one-
impurities each electron transfer starts a chain. Control of chain dimensional conductivity in the direction of the long axis is only
length may be done by addition of a small amount of proton donor two orders of magnitude lower than that of iron. The increase in
or by interposing a pattern of negative and positive pulses separated conductivity is attributed to the high unidirectional polarizability of
by a chosen time interval. Such a pattern of pulses initiates a chain, DNA.218
lets it grow to a certain length, and the chain is terminated by the It has been suggested that the high ability to conduct holes is
positive pulse. Examples of monomers electrochemically polymer- developed to protect essential parts of DNA against oxidation by
ized are styrene,196 phenylacetylenes,197 propylene oxide,198 and transferring the attacking hole to a less essential part of the genome.
methyl methacrylate.199 Of the four bases guanine is more easily oxidized than the three
The finding that polyacetylene on oxidation with iodine changed others 关E 共pH 7兴: G 1.04 V, T 1.29 V, A 1.32 V, and C 1.44 V vs.
the polymer from an insulator to a material with nearly metallic
NHE兲219,220 and by having long stretches of GC without essential
conductivity200 initiated much research on conducting polymers, at
function in the cell and good conductivity, the damaging hole may
first primarily to develop a rechargeable battery. It was found that
be transferred to the more easily oxidized part of the genome, and
besides polyacetylene,201 polypyrrole,202 polythiophene,203 and
the hole may end by oxidizing guanine to 7,8-dihydro-8-
polyaniline204 could be made electrical conducting by ‘‘doping’’
oxoguanine. G is not only the most easily oxidizable base, but its
which in this context is a redox reaction; p-doping corresponds to an
catalytic one-electron oxidation in poly-G sequences is particular
oxidation and n-doping to a reduction.
fast. The sacrificially oxidized protective domain may subsequently
Conducting polymers differ from redox polymers in that in con-
be excised and repaired.221 The function of the sacrificial stretches
ducting polymers the monomers interact via a ␲-electron system
of guanine to protect the essential part of the genome has been
whereas the chain in a redox polymer is not conjugated. compared to the cathodic protection of iron by zinc; a review of this
The polymerization of pyrrole begins with an oxidation to the hypothesis has recently appeared.222
radical cation; two of these dimerize with a rate constant205 of about
109 M⫺1 s⫺1 and the dimerized species loses two protons. The Metalorganic compounds.—Organoelemental compounds exist of
dimerization takes place at the ␣-positions of the radical cations. many elements of the periodic table and only a few investigations
The radical cation of the dimer and especially the tetramer reacts can be presented here. Reviews of the electrochemistry of such com-
slower, so a radical cation reacts faster with another radical cation pounds have been published.223-225
than with the dimer or tetramer. The rate of the dimerization206 of One of the most investigated organometallic compounds is fer-
the radical cation of thiophene tetramer is only about 105 M⫺1 s⫺1 . rocene; it is reversibly oxidized to ferrocenium, and as the solvation
These results and results obtained by Heinze207 with energy of the system is low, it has been recommended as a standard
3-methylthiophene indicate that the system to compare potentials in different solvent systems.226 Fer-
rocene has been prepared electrochemically using an iron anode and
cathodically generated cyclopentadiene anion.227 Metallocenes may
be used in indirect reactions, for instance as a mediator for the
regeneration of FAD.
Metal complexes of porphine-type compounds, the so-called pig-
ments of life, have been investigated intensively; the electrochemis-
try of metalloporphyrins in nonaqueous media has been reviewed by
Kadish.228
The cobalt-complex vitamin B12 and related compounds have
been investigated by Savéant229 by different techniques with deter-
mination of rate constants for cleavage and formation reactions and
constants for complex formation. Vitamin B12 has preparatively
been used for the catalysis of different reactions by Scheffold.230
polymerization does not take place by chain propagation, adding a Reduction of the Co共III兲-derivative of vitamin B12 cleaves the axial
monomer to a growing chain. ligand with further reduction to the Co共I兲-derivative. This compound
The charging process of conducting polymers has been suggested can add an alkyl halide RX in an oxidative addition. The RCo共III兲
to involve two coexisting subsystems at the polymer matrix; one compound loses on reduction the radical R • which may add to an
system to exchange electrons with the electrode in a quasi-reversible activated alkene; oxidative addition of RX to the Co共I兲 derivative
manner and another system which involves chemically reversible forming RCo共III兲 completes the catalytic circle. The product is thus
intermolecular bonds between neighboring polymer molecules.208 akin to a Michael addition of R⫺ to the alkene.
On oxidation or reduction of the insulating polymer to a conduct- A similar catalytic circle in which primary and secondary alkyl
ing polymer, the polymer get a charge which requires the diffusion radicals, formed by reducing a RNi共II兲 complex, are added to an
of counter ions. This has to be taken into account in practical appli- activated olefin may be achieved; oxidative addition of RX to the
cations and in all theoretical treatments of the electropolymerization. Ni共0兲 complex reforms the RNi共II兲 complex and completes the cata-
S30 Journal of The Electrochemical Society, 149 共4兲 S21-S33 共2002兲

lytic circle.231 Another reaction with carbon-carbon bond formation The use of divided cells with membranes causes many problems
is the Pd(PPh3 ) 4 -catalyzed synthesis of biaryls from aryl bromides when non-aqueous solvents have to be employed, and sacrificial
and iodides.232,233 and the Cu共II兲 salt-catalyzed reaction of alkenyl- anodes in an undivided cell may be an alternative. This has been
stananes to symmetrical dienes in a homocoupling with high used in the production of Fenoprofen which is prepared by reduction
stereospecificity.234 of chloroethyldiphenyl ether in N,N-dimethylformamide under a
Silicon and tin compounds have been used in different contexts. carbon dioxide pressure of 2 bar. The carbanion formed in the re-
Silicon interacts effectively with a neighboring ␲-orbital or p-orbital duction reacts with carbon dioxide to form the carboxylic acid.241,242
at a heteroatom and increases the HOMO level and thus lowers the
oxidation potential. Oxidation of an allylsilane proceeds smoothly C6 H5 -O-C6 H4 -CHCl-CH3 ⫹ 2 e ⫹ CO2
with cleavage of the C-Si bond and further oxidation of the radical → C6 H5 -O-C6 H4 -CH共 COO⫺兲 -CH3 ⫹ Cl⫺
to the cation which reacts with a nucleophile in both allylic
positions.235 The silanes may be prepared by reduction of an organic
The dream of an organic electrochemist has always been to make
halide in the presence of chlorosilane236,237 useful products simultaneously at the cathode and the anode. Some
laboratory examples have been published,243 but only recently has
RCH⫽C共 R⬘ 兲 -CH2 SiMe3 ⫺ e → RCH⫽C共 R⬘ 兲 CH⫹
2 ⫹ 共 Nu 兲 an industrial ‘‘paired synthesis’’ been realized by BASF.244 In an
→ RCH共 Nu兲 CR⬘ ⫽CH2 undivided cell using methanol as solvent, phthalic acid dimethyl
ester is cathodically reduced to phthalide and at the anode 4-tert-
⫹ RCH⫽C共 R⬘ 兲 CH2 Nu butyltoluene is oxidized to 4-tert-butylbenzaldehyde dimethylacetal;
the methanol released at the cathode is used at the anode to form the
dimethylacetal. Previously phthalic acid anhydride was reduced
When a stannyl and a silyl group are situated at the same carbon catalytically to phthalide and the anodic oxidation of 4-tert-
atom, the CuSn bond is cleaved at a lower oxidation potential than butyltoluene gave dihydrogen as biproduct; the paired synthesis
the CuSi bond. The CuSi bond may then be cleaved by raising avoids high pressure catalytic hydrogenation and the energy demand
the potential and another nucleophile can be introduced.238 When a has been drastically reduced.
Si or Sn group has been used to modify the potential, it has been
termed an electroauxilary group.
Industrial processes.—In the mid-sixties two commercial processes
were introduced: the Nalco process for the production of tetraalkyl
lead239 and Monsanto’s production of adiponitrile240 by reductive
dimerization of acrylonitrile, the latter process developed by Manuel
M. Baizer. The successful introduction of these two productions
increased substantially the interest of chemical companies to con-
sider development of industrial electrochemical reactions.
The key to the success of the Monsanto process was Baizer’s
discovery that the use of tetraalkylammonium salts as supporting
electrolyte in water as solvent created a layer at the cathode in which
the proton activity was low enough to avoid a protonation of the
radical anion faster than its dimerization but high enough to proto-
References
nate the dimerized product and thus avoid a base-catalyzed polymer-
ization of acrylonitrile. 1. A. G. A. Volta, J. Nat. Phil. Chem. Arts, 4, 179 共1800兲.
2. M. Faraday, Ann. Phys. (Leipzig), 47, 438 共1834兲.
The first Monsanto process used a divided cell with lead elec- 3. J. Kolbe, J. Prakt. Chem., 41, 138 共1847兲.
trodes 共the anode with 1 % Ag兲 and an ion-exchange membrane as 4. A. Crum Brown and J. Walker, Liebigs Ann. Chem., 261, 107 共1891兲; A. Crum
separator, but it was soon realized that it was possible to use an Brown and J. Walker, Liebigs Ann. Chem., 274, 41 共1893兲.
undivided cell which improved the economy, although the selectiv- 5. Ch. F. Schoenbein, Liebigs Ann. Chem., 54, 164, 176 共1845兲.
6. F. Haber, Z. Elektrochem. Angew. Phys. Chem., 5, 235 共1898兲.
ity was slightly lower 共88 vs. 92兲 and the current density had to be 7. F. Fichter, Organische Elektrochemie, Steinkopff, Dresden 共1942兲.
halved. However, the electrode distance was diminished from 7 to 8. S. Swann, Jr., Trans. Electrochem. Soc., 69, 287 共1936兲; S. Swann, Jr., Trans.
1.8 mm, the necessary voltage was lowered from 11.6 V to 3.8 V, so Electrochem. Soc., 77, 459 共1940兲.
the energy consumption declined from 6700 to 2500 kWh/ton. The 9. M. Le Blanc, Z. Elektrochem. Angew. Phys. Chem., 7, 292 共1900兲.
10. R. L. Taylor, Chem. Metall. Eng., 44, 588 共1937兲.
cathode material was cadmium with carbon steel as anode. The elec- 11. J. Heyrovsky, Chem Listy, 16, 256 共1922兲; J. Heyrovsky, Philos. Mag., 45, 303
troreductive dimerization of acrylonitrile is now carried out by sev- 共1923兲.
eral companies and the volume of the production is about 300 000 12. M. Shikata, Trans. Faraday Soc., 21, 42, 53 共1925兲.
t/yr. 13. J. Heyrovsky and M. Shikata, Recl. Trav. Chim. Pays-Bas., 44, 496 共1925兲.
14. J. Heyrovsky and I. Smoler, Collect. Czech. Chem. Commun., 4, 521 共1932兲.
In the Nalco process a Grignard reagent is made from an alkyl 15. A. Winkel and G. Proske, Ber. Dtsch. Chem. Ges. B, 69, 693, 1917 共1936兲.
chloride and magnesium in an ether solution, and the Grignard re- 16. G. Semerano and A. Chisine, Gazz. Chim. Ital., 66, 504 共1936兲.
agent, RMgCl, is oxidized at a sacrificial lead anode. The radicals 17. R. Brdicka, Collect. Czech. Chem. Commun., 5, 238 共1933兲; R. Brdicka, Collect.
attack the lead with formation of tetraalkyllead. At the cathode mag- Czech. Chem. Commun., 8, 366 共1936兲.
18. I. M. Kolthoff and S. C. Miller, J. Am. Chem. Soc., 62, 2171 共1940兲.
nesium salt is reduced to magnesium which reacts with the alkyl 19. I. M. Kolthoff and J. J. Lingane, Polarography, Interscience, New York 共1941兲.
chloride to form the Grignard reagent. The process was run for 20. J. Heyrovsky, Polarographie, Springer, Wien, 1941.
about 20 years, but was abandoned in the early nineteen eighties due 21. H. A. Laitinen and S. Wawzonek, J. Am. Chem. Soc., 64, 1765 共1942兲; S. Waw-
to the diminished use of tetraalkyllead in gasoline zonek and H. A. Laitinen, J. Am. Chem. Soc., 64, 2365 共1942兲.
22. M. von Stackelberg and W. Stracke, Z. Elektrochem. Angew. Phys. Chem., 53, 118
共1949兲.
4 Mg ⫹ 4 EtCl → 4 EtMgCl 23. F. Petru, Collect. Czech. Chem. Commun., 12, 620 共1947兲.
24. R. M. Elofson, R. L. Edsberg, and P. A. Mecherly, J. Electrochem. Soc., 97, 166
共1950兲
4 EtMgCl ⫺ 4 e ⫹ 4 Cl⫺ → 4 Et• ⫹ 4 MgCl2 25. P. C. Tompkins and C. L. A. Schmidt, J. Biol. Chem., 143, 643 共1942兲; P. C.
Tompkins and C. L. A. Schmidt, Univ. Calif. Pub. Physiol., 8, 237, 247 共1944兲.
4 Et. ⫹ Pb → Et4 Pb 26. J. T. Stock, J. Chem. Soc., 1944, 427; J. T. Stock, J. Chem. Soc., 1949, 763.
27. J. J. Lingane, C. G. Swain, and M. Fields, J. Am. Chem. Soc., 65, 1348 共1943兲.
28. A. Hickling, Trans. Faraday Soc., 38, 27 共1942兲.
MgCl2 ⫹ 2 e → Mg ⫹ 2 Cl⫺ 29. J. J. Lingane and S. L. Jones, Anal. Chem., 22, 1169 共1950兲.
Journal of The Electrochemical Society, 149 共4兲 S21-S33 共2002兲 S31

30. J. Heyrovsky and J Kuta, Grundlagen der Polarographie, Akademie-Verlag, Ber- 80. H. Carrero, J. Gao, J. F. Rusling, C.-W. Lee, and A. J. Fry, Electrochim. Acta, 45,
lin 共1965兲. 503 共1999兲.
31. I. M. Kolthoff and J. J. Lingane, Polarography, 2nd ed., Wiley-Interscience, New 81. G. Silvestri, S. Gambino, and G. Filardo, Adv. Polym. Sci., 38, 28 共1981兲; G.
York 共1952兲. Silvestri, S. Gambino, and G. Filardo, Acta Chem. Scand., 45, 987 共1991兲.
32. L. Meites, Polarographic Techniques, 2nd ed., Wiley-Interscience, New York 82. O. Sock, M. Troupel, and J. Perichon, Tetrahedron Lett., 26, 1509 共1985兲; C.
共1965兲. Saboureaum, M. Troupel, and J. Perichon, J. Appl. Electrochem., 20, 97 共1990兲.
33. M. Brezina and P. Zuman, Polarography in Medicine, Biochemistry and Phar- 83. R. F. Lane and A. T. Hubbard, J. Phys. Chem., 77, 1401, 1411 共1973兲.
macy, Wiley-Interscience, New York 共1958兲. 84. B. F. Watkins, J. R. Behling, E. Kariv, and L. L. Miller, J. Am. Chem. Soc., 97,
34. P. Zuman, Substituent Effects in Organic Polarography, Plenum, New York 3549 共1975兲.
共1967兲. 85. J. C. Lennox and R. W. Murray, J. Electroanal. Chem., 78, 395 共1977兲; J. R.
35. H. Matsuda and Y. Ayabe, Z. Elektrochem., 59, 494 共1955兲. Lenhard and R. W. Murray, J. Am. Chem. Soc., 100, 7870 共1978兲.
36. H. Lund, Acta Chem. Scand., 11, 491, 1323 共1957兲. 86. C. A. Koval and F. C. Anson, Anal. Chem., 50, 223 共1978兲.
37. J. H. Simons, J. Electrochem. Soc., 95, 47 共1949兲. 87. G. Bidan, A. Deronzier, and J.-C. Moutet, J. Chem. Soc. Chem. Commun., 1984,
38. H. Meinert, R. Fackler, J. Mader, P. Reuter, and W. Roehlke, J. Fluorine Chem., 1185; S. Cosnier, A. Deronzier, and J.-C. Moutet, J. Electroanal. Chem., 193, 193
51, 53 共1991兲. 共1985兲.
39. S. Rüdiger, A. Dimitrov, and K. Hottmann, J. Fluorine Chem., 76, 155 共1996兲. 88. J. G. Eaves and H. S. Munro, J. Chem. Soc. Chem. Commun., 1985, 684.
40. P. Sartori and N. Ignat’ev, J. Fluorine Chem., 87, 157 共1998兲. 89. F. A. Armstrong, R. Camba, H. A. Heering, J. Hirst, L. J. C. Jeuken, A. K. Jones,
41. V. Childs, C. Gross, and S. Polson, Abstract 1006, The Electrochemical Society C- Léger, and J. P. McEvoy, Faraday Discuss., 116, 191 共2000兲.
Meeting Abstracts, Seattle, WA, May 2-6, 1999. 90. E. A. G. Hall, Biosensors, Prentice-Hall, Upper Saddle River, NJ 共1991兲.
42. I. N. Rozhkov and I. L. Knunyants, Dokl. Akad. Nauk SSSR, 199, 614 共1971兲; I. 91. V. J. Puglisi and A. J. Bard, J. Electrochem. Soc., 119, 829 共1972兲; V. J. Puglisi
N. Rozhkov and I. L. Knunyants, Chem. Abstr., 76, 7291 共1972兲. and A. J. Bard, J. Electrochem. Soc., 120, 748 共1973兲.
43. H. Schmidt and H. D. Schmidt, Chem. Tech. (Leipzig), 5, 454 共1953兲; H. Schmidt 92. E. Lamy, L. Nadjo, and J.-M. Savéant, J. Electroanal. Chem., 42, 189 共1973兲; E.
and H. D. Schmidt, J. Prakt. Chem., 2, 105 共1955兲. Lamy, L. Nadjo, and J.-M. Savéant, J. Electroanal. Chem., 50, 141 共1974兲.
44. T. Fuchigami, in Organic Electrochemistry, 4th ed., H. Lund and O. Hammerich, 93. R. D. Grypa and J. T. Maloy, J. Electrochem. Soc., 122, 509 共1975兲; B. M. Bezilla
Editors, p. 1035, Marcel Dekker, New York 共2001兲. and J. T. Maloy, J. Electrochem. Soc., 126, 579 共1979兲.
45. N. Clauson-Kaas, F. Limborg, and K. Glens, Acta Chem. Scand., 6, 531 共1952兲; 94. J.-M. Savéant, Acta Chem. Scand., B37, 365 共1983兲; C. Amatore, J. Pinson, and
N. Clauson-Kaas and Z. Tyle, Acta Chem. Scand., 6, 962 共1952兲. J.-M. Savéant, J. Electroanal. Chem., 137, 143 共1982兲.
46. S. W. Feldberg in Electroanalytical Chemistry, Vol. 3, A. J. Bard, Editor, p. 199 95. V. D. Parker, Acta Chem. Scand., B35, 147,149 共1981兲; V. D. Parker, Acta Chem.
共1969兲; M. Rudolph, D. P. Reddy, and S. W. Feldberg, Anal. Chem., 66, A589 Scand., B37, 393 共1983兲; O. Hammerich and V. D. Parker, Acta Chem. Scand.,
共1994兲. B37, 379 共1983兲.
47. D. Britz, Digital Simulation in Electrochemistry, 2nd ed., Springer, Berlin 共1988兲. 96. V. D. Parker, Acta Chem. Scand., B35, 147 共1981兲.
48. A. J. Bard and L. R. Faulkner, Electrochemical Methods, John Wiley & Sons, 97. I. Fussing, O. Hammerich, A. Hussain, M. F. Nielsen, and J. H. P. Utley, J. Chem.
New York 共1999兲. Soc., Perkin Trans. 2, 1996, 649.
49. C. P. Andrieux and J.-M. Savéant, in Investigations of Rates and Mechanisms of 98. I. Fussing, O. Hammerich, A. Hussain, M. F. Nielsen, and J. H. P. Utley, Acta
Reaction, C. F. Bernasconi, Editor, p. 305, John Wiley & Sons, New York 共1986兲. Chem. Scand., 52, 328 共1998兲.
50. S. U. Pedersen and K. Daasbjerg, Electrochemical Techniques in Electron Trans-
99. M. M. Baizer and J. L. Cruma, J. Org. Chem., 37, 1951 共1972兲.
fer in Chemistry, Vol. 1, Z. B. Balzani, Editor, John Wiley & Sons, New York
100. J. H. Wagenknecht, J. Electroanal. Chem., 52, 489 共1974兲.
共2001兲.
101. G. Silvestri, S. Gambino, G. Filardo, and A. Gulotta, Angew. Chem. Int. Ed. Engl.,
51. O. Hammerich, in Organic Electrochemistry, 4th ed., H. Lund and O. Hammerich,
23, 979 共1984兲.
Editors, Marcel Dekker, New York 共2001兲.
102. J. F. Fauvarque, Y. de Zelicourt, C. Amatore, and A. Jutand, J. Appl. Electrochem.,
52. J.-M. Savéant and E. Vianello, C. R. Acad. Sci. URSS, 256, 2597 共1963兲.
20, 338 共1990兲.
53. R. S. Nicholson and I. Shain, Anal. Chem., 36, 706 共1964兲; R. S. Nicholson and I.
103. F. Köster, E. Dinjus, and E. Dunach, Eur. J. Org. Chem., 2001, 2507.
Shain, Anal. Chem., 37, 178, 190 共1965兲; R. S. Nicholson, Anal. Chem., 37, 1351
104. M. Troupel, Y. Rollin, J. Perichon, J. Fauvarque, Nuov. J. Chim., 5, 621 共1981兲.
共1965兲.
105. A. Gennaro, A. A. Isse, and F. Maran, J. Electroanal. Chem., 507, 124 共2001兲.
54. J. C. Imbeaux and J.-M. Savéant, J. Electroanal. Chem., 28, 325 共1970兲; D.
106. S. Olivero and E. Dunach, Eur. J. Org. Chem., 1999, 1885.
Garreau and J.-M. Savéant, J. Electroanal. Chem., 86, 63 共1978兲.
107. D. P. Fox, R. D. Little, and M. M. Baizer, J. Org. Chem., 50, 2202 共1985兲.
55. S. Antonello, M. Musumeci, D. D. M. Wayner, and F. Maran, J. Am. Chem. Soc.,
108. N. T. Nugent, M. M. Baizer, and R. D. Little, Tetrahedron Lett., 23, 1339 共1982兲.
119, 9441 共1997兲.
56. M. Fleishman, S. Pons, R. Rolison, and P. P. Schmidt, Ultramicroelectrodes, 109. T. Shono and M. Mitani, J. Am. Chem. Soc., 93, 5284 共1971兲.
Datatech Systems, New York 共1987兲. 110. H. Lund and L. G. Feoktistov, Acta Chem. Scand., 23, 3482 共1969兲.
57. C. P. Andrieux, D. Garreau, P. Hapiot, and J.-M. Savéant, J. Electroanal. Chem., 111. H. Lund, in Advances in Heterocyclic Chemistry, A. R. Katritzky and A. J. Boul-
248, 447 共1988兲. ton, Editors, p. 12, Academic Publishers, New York 共1970兲; H. Lund and I. Taba-
58. D. O. Wipf and R. M. Wightman, J. Phys. Chem., 93, 4286 共1989兲. kovic, in Advances in Heterocyclic Chemistry, A. R. Katritzky and A. J. Boulton,
59. C. Amatore, E. Maisonhaute, and G. Siminneau, Electrochem. Commun., 2, 81 Editors, p. 36, Academic Publishers, New York 共1970兲; H. Lund in Organic Elec-
共2000兲; C. Amatore, E. Maisonhaute, and G. Siminneau, J. Electroanal. Chem., trochemistry, H. Lund and O. Hammerich, Editors, p. 669, Marcel Dekker, New
486, 141 共2000兲. York 共2001兲.
60. F. Zhou and A. J. Bard, J. Am. Chem. Soc., 116, 393 共1994兲. 112. R. Hazard and A. Tallec, Bull. Soc. Chim. Fr., 1973, 3040; M. Cariou, R. Hazard,
61. D. A. Treichel, M. V. Mirkin, and A. J. Bard, J. Phys. Chem., 98, 5751 共1994兲. M. Jubault, and A. Tallec, Can. J. Chem., 61, 2359 共1983兲.
62. F.-R. Fan and A. J. Bard, Science, 267, 871 共1995兲. 113. W. J. Begley, J. Grimshaw, and J. Trocha-Grimskaw, J. Chem. Soc., Perkin Trans.
63. T. Solomon and A. J. Bard, J. Phys. Chem., 99, 17487 共1995兲. 1, 1974, 2633; M. Dias, M. Gibson, J. Grimshaw, I. Hill, J. Trocha-Grimshaw, and
64. A. L. Parker, P. R. Unwin, and J. Zhang, Electrochem. Commun., 3, 372 共2001兲. O. Hammerich, Acta Chem. Scand., 52, 549 共1998兲.
65. B. Liu, S. A. Rotenberg, and M. V. Mirkin, Proc. Natl. Acad. Sci. U.S.A., 97, 9855 114. K. Sasaki, H. Urata, K. Uneyama, and S. Nagura, Electrochim. Acta, 12, 137
共2000兲. 共1967兲.
66. M. V. Mirkin, B. Liu, and S. A. Rosenberg, 22nd Sandbjerg Meeting Abstracts, p. 115. V. D. Parker and B. B. Burgert, Tetrahedron Lett., 1968, 2415.
30 共2001兲. 116. A. Nilsson, U. Palmquist, T. Petterson, and A. Ronlán, J. Chem. Soc., Perkin
67. C. Amatore, S. Arbault, D. Bruce, P. de Oliveira, M. Erard, and M. Vuillaume, Trans. 1, 1978, 708.
Faraday Discuss., 116, 319 共2000兲. 117. S. D. Ross, M. Finkelstein, and R. C. Petersen, J. Am. Chem. Soc., 88, 4657
68. L. Eberson, M. P. Hartshorn, J. J. McCullough, O. Persson, and F. Radner, Acta 共1966兲; E. J. Rudd, M. Finkelstein, and S. D. Ross, J. Org. Chem., 37, 1763
Chem. Scand., 52, 1024 共1998兲; L. Eberson, M. P. Hartshorn, F. Radner, and O. 共1972兲.
Persson, J. Chem. Soc., Perkin Trans. 2, 1998, 59. 118. T. Shono, Y. Matsumura, K. Tsubuta, Y. Sugihara, S. Yamane, T. Kanazawa, and T.
69. S. Wawzonek and M. E. Runner, J. Electrochem. Soc., 99, 457 共1952兲; I. M. Aoki, J. Am. Chem. Soc., 104, 6697 共1982兲; T. Shono, Y. Matsumura, K. Tsubata,
Kolthoff and J. F. Coetzee, J. Am. Chem. Soc., 79, 870, 1852 共1958兲. and K. Uchida, J. Org. Chem., 51, 2590 共1986兲.
70. J. Phelps, K. S. V. Santhanam, and A. J. Bard, J. Am. Chem. Soc., 89, 1752 共1967兲. 119. K. D. Mueller, Tetrahedron, 56, 9527 共2000兲; H. K. Reddy, K. Chiba, Y. Sun, and
71. O. Hammerich and V. D. Parker, Electrochim Acta., 18, 537 共1973兲. K. D. Mueller, Tetrahedron, 57, 5183 共2001兲.
72. E. Garcia and A. J. Bard, J. Electrochem. Soc., 137, 2752 共1990兲. 120. T. Siu, W. Li, and A. K. Yudin, J. Comb. Chem., 2, 545 共2000兲; A. K. Yudin and
73. R. S. Glass and V. V. Jouikov, Tetrahedron Lett., 40, 6357 共1999兲. T. Siu, Curr. Opin. Chem. Biol., 5, 269 共2001兲.
74. N. S. Moe, Acta Chem. Scand., 21, 1389 共1967兲. 121. L. Eberson, J. Am. Chem. Soc., 89, 4669 共1967兲; L. Eberson, Tetrahedron, 32,
75. C. Amatore, M. A. Oturan, J. Pinson, J.-M. Savéant, and A. Thiebault, J. Am. 2185 共1976兲.
Chem. Soc., 107, 3451 共1985兲; C. Combellas, F. Kanoufi, and A. Thiebault, J. 122. D. B. Clark, M. Fleischman, and D. Pletcher, J. Chem. Soc., Perkin Trans. 2,
Electroanal. Chem., 407, 195 共1996兲. 1973, 1578.
76. R. A. Benkeser and E. M. Kaiser, J. Am. Chem. Soc., 85, 2858 共1963兲. 123. E. Klocke, A. Matzeit, M. Gockeln, and H. J. Schäefer, Chem. Ber., 126, 1623
77. C. A. Nelson and A. Benton, J. Electroanal. Chem., 202, 253 共1986兲. 共1993兲.
78. G. J. Gordillo and D. J. Schiffrin, J. Chem. Soc., Faraday Trans., 90, 1913 共1994兲; 124. H. J. Schäfer, Angew. Chem. Int. Ed. Engl., 20, 911 共1981兲.
G. J. Gordillo and D. J. Schiffrin, Faraday Discuss., 116, 89 共2000兲. 125. M. Feldhues and H. J. Schäfer, Tetrahedron, 41, 4195, 4213 共1985兲.
79. G. N. Kamau and J. F. Rusling, Langmuir, 12, 2645 共1996兲; X. Zu and J. F. 126. L. Becking and H. J. Schäfer, Tetrahedron Lett., 29, 2797, 2801 共1988兲.
Rusling, Langmuir, 13, 3693 共1997兲. 127. R. N. Renaud, P. J. Champagne, and M. Savard, Can. J. Chem., 57, 2627 共1979兲.
S32 Journal of The Electrochemical Society, 149 共4兲 S21-S33 共2002兲

128. N. Muller, J. Org. Chem., 48, 1370 共1983兲: N. Muller, J. Org. Chem., 49, 2826, 170. T. Shono, S. Kashimura, and H. Nogusa, J. Org. Chem., 49, 2043 共1984兲.
4559 共1984兲; N. Muller, J. Org. Chem., 51, 263 共1986兲. 171. T. Shono, N. Kise, M. Masuda, and T. Suzumoto, J. Org. Chem., 50, 2527 共1985兲.
129. M. Yoshikawa, T. Kamigauchi, Y. Iked, and I. Kitagawa, Chem. Pharm. Bull. 172. D. H. Chin, G. Chiericato, E. J. Nanni, and D. T. Sawyer, J. Am. Chem. Soc., 104,
(Tokyo), 29, 2582 共1981兲. 1296 共1982兲.
130. D. Seebach, R. Charczuk, C. Gerber, P. Renaud, H. Berner, and H. Schneider, 173. M. Sugawara, M. M. Baizer, W. T. Monte, R. D. Little, and U. Hess, J. Am. Chem.
Helv. Chim. Acta, 72, 419 共1989兲. Soc., B37, 509 共1983兲.
131. D. H. Evans, P. Jimenez, and M. J. Kelly, J. Electroanal. Chem., 163, 145 共1984兲. 174. Z. I. Niazimbetova, D. H. Evans, L. M. Liable-Sands, and A. L. Rheingold, J.
132. R. A. Marcus, Annu. Rev. Phys. Chem., 15, 155 共1964兲. Electrochem. Soc., 147, 256 共2000兲.
133. C. L. Wong and J. K. Kochi, J. Am. Chem. Soc., 101, 5593 共1979兲; S. Fukuzumi, 175. H. Sagae, M. Fujihira, H. Lund, and T. Osa, Bull. Chem. Soc. Jpn., 53, 1537
C. L. Wong, and J. K. Kochi, J. Am. Chem. Soc., 102, 2928 共1980兲. 共1980兲.
134. L. Eberson, Electron Transfer Reactions in Organic Chemistry, Springer, Berlin 176. J. Pinson and J.-M. Savéant, J. Chem. Soc. Chem. Commun., 1974, 933; J. Pinson
共1987兲. and J.-M. Savéant, J. Am. Chem. Soc., 100, 1507 共1978兲, J.-M. Savéant, Acc.
135. J. R. Miller, L. T. Calcaterra, and G. L. Closs, J. Am. Chem. Soc., 106, 3047 Chem. Res., 13, 323 共1980兲.
共1984兲. 177. J. E. Swartz and T. T. Stenzal, J. Am. Chem. Soc., 106, 2520 共1984兲.
136. I. R. Gould, J. E. Moser, D. Ege, and S. Farid, J. Am. Chem. Soc., 110, 1991 178. N. Alam, C. Amatore, C. Combellas, A. Thiebault, and J. N. Verpeaux, Tetrahe-
共1988兲; I. A. Gould, R. Moody, and S. Farid, J. Am. Chem. Soc., 110, 7242 共1988兲. dron Lett., 49, 6171 共1987兲.
137. C. P. Andrieux, J. M. Dumas-Bouchiat, and J.-M. Savéant, J. Electroanal. Chem., 179. C. Costentin, P. Hapiot, M. Medebielle, and J.-M. Savéant, J. Am. Chem. Soc.,
87, 39, 55 共1978兲; C. P. Andrieux, J. M. Dumas-Bouchiat, and J.-M. Savéant, J. 121, 4451 共1999兲, 122, 5623 共2000兲.
Electroanal. Chem., 88, 43 共1978兲. 180. T. Lund and H. Lund, Acta Chem. Scand., B40, 470 共1986兲; T. Lund and H. Lund,
138. J. W. Sease and R. C. Reed, cited in A. J. Fry, Synthetic Organic Electro- Acta Chem. Scand., B41, 93 共1987兲; T. Lund and H. Lund, Acta Chem. Scand.,
chemistry, Harper & Row, 1972, p. 67; J. W. Sease and R. C. Reed, Tetrahedron B42, 269 共1988兲.
Lett., 1975, 393. 181. H. Lund, K. Daasbjerg, T. Lund, and S. U. Pedersen, Acc. Chem. Res., 28, 313
139. H. Lund, M.-A. Michel, and J. Simonet, Acta Chem. Scand., B28, 900 共1974兲; H. 共1995兲.
Lund, M.-A. Michel, and J. Simonet, Acta Chem. Scand., B29, 217 共1975兲; J. 182. L. Horner and D. Degner, Tetrahedron Lett., 1968, 5889; 1245 共1971兲, Electro-
Simonet, M.-A. Michel, and H. Lund, Acta Chem. Scand., B29, 489 共1975兲. chim. Acta, 19, 611 共1974兲; L. Horner and D. H. Skaletz, Liebigs Ann. Chem.,
140. H. Lund and J. Simonet, J. Electroanal. Chem., 65, 205 共1975兲. 1977, 1365.
141. V. G. Mairanovskii and N. F. Loginova, Zh. Obshch. Khim., 45, 2112 共1975兲; V. 183. D. Seebach and H. A. Oei, Angew. Chem., 87, 629 共1975兲.
G. Mairanovskii, Angew. Chem. Int. Ed. Engl., 15, 281 共1976兲. 184. R. N. Gourley, J. Grimshaw, and P. G. Millar, J. Chem. Soc. Chem. Commun.,
142. P. E. Hansen, A. Berg, and H. Lund, Acta Chem. Scand., B30, 267 共1976兲; E. 1967, 1278 共1967兲: R. N. Gourley, J. Grimshaw, and P. G. Millar, J. Chem. Soc.,
Hobolth and H. Lund, Acta Chem. Scand., B30, 895 共1976兲. 1970, 2318.
143. H. Lund, K. Daasbjerg, D. Occhialini, and S. U. Pedersen, Elektrokhimiya, 31, 185. R. Hazard, S. Jaouannet, and A. Tallec, Tetrahedron, 38, 93 共1982兲,
939 共1995兲. 186. N. Schoo and H. J. Schäfer, Liebigs Ann. Chem., 1993, 609; M. F. Nielsen, B.
144. J. Simonet and H. Lund, Acta Chem. Scand., B31, 909 共1977兲. Batanero, S. Rolvering, and H. J. Schäfer, in Novel Trends in Electroorganic
145. C. Gosden, K. P. Healy, and D. Pletcher, J. Chem. Soc. Dalton Trans., 1978, 972. Synthesis, S. Torii, Editor, Springer, Tokyo 共1998兲.
146. J. J. Pietron and R. W. Murray, J. Phys. Chem. B, 103, 4440 共1999兲. 187. J. Hermolin, J. Kopilev, and E. Gileadi, J. Electroanal. Chem., 71, 245 共1976兲.
147. M. Brust, M. Walker, D. Bethell, D. J. Schiffrin, and R. Whyman, J. Chem. Soc. 188. H. Wendt, Angew. Chem. Int. Ed. Engl., 21, 256 共1982兲.
Chem. Commun., 1994, 801. 189. B. F. Watkins, J. R. Behling, E. Kariv, and L. L. Miller, J. Am. Chem. Soc., 97,
148. R. S. Ingram and R. W. Murray, Langmuir, 14, 4115 共1998兲. 3549 共1975兲; B. E. Firth, L. L. Miller, M. Mitani, T. Rogers, J. Lennox, and R. W.
149. A. C. Templeton, W. P. Wuelfing, and R. W. Murray, Acc. Chem. Res., 33, 27 Murray, J. Am. Chem. Soc., 98, 8271 共1976兲.
共2000兲. 190. S. Abe, T. Nonaka, and T. Fuchigami, J. Am. Chem. Soc., 105, 3630 共1083兲, T.
150. W. Schuhmann, H. Zimmermann, K. Habermüller, and V. Laurinaviciuc, Faraday Komoti and T. Nonaka, J. Am. Chem. Soc., 106, 2656 共1984兲.
Discuss., 116, 245 共2000兲. 191. T. Osa, Y. Kashiwagi, Y. Yanagisawa, and J. M. Bobbitt, J. Chem. Soc. Chem.
151. M. E. Hermandez and D. K. Newman, Cell. Med. Life Sci., 58, 1662 共2001兲. Commun., 1994, 2535.
152. C.-H. Lee, T. A. Lewis, A. Paszczynski, and R. L. Crawford, Biochem. Biophys. 192. Y. Kashiwagi, Q. Pan, F. Kurashima, C. Kikuchi, J.-i. Anzai, and T. Osa, Chem.
Res. Commun., 261, 562 共1999兲. Lett., 1998, 143.
153. W. Schmidt and E. Steckhan, Chem. Ber., 113, 577 共1980兲; M. Platen and E. 193. P. N. Bartlett, D. Pletcher, and J. Zeng, J. Electrochem. Soc., 144, 3705 共1997兲.
Steckhan, Liebigs Ann. Chem., 1984, 1563. 194. E. Steckhan, Top. Curr. Chem., 170, 83 共1994兲; E. Steckhan, GDCh Monographie,
154. T. Douadi, M. Cariou, and J. Simonet, Tetrahedron, 52, 4449 共1996兲; T. Douadi, 9, 483 共1996兲, Gesellschaft Deutcher Chemiker, Frankfurt/Main, 1997.
M. Cariou, and J. Simonet, New J. Chem., 20, 1031 共1996兲. 195. E. Steckhan, in Electroenzymatic Synthesis in Organic Electrochemistry, 4th ed.,
155. C. E. Lomen, W. U. de Alwis, and G. S. Wilson, J. Chem. Soc., Faraday Trans. 1, H. Lund and O. Hammerich, Editors, Marcel Dekker, New York 共2001兲.
82, 1265 共1986兲. 196. B. L. Funt and K. C. Yu, J. Polym. Sci., 62, 359 共1962兲.
156. C. Bourdillon, C. Demaille, J. Moiroux, and J.-M. Savéant, Acc. Chem. Res., 29, 197. C. Simionescu and M. Grovu, Angew. Makromol. Chem., 111, 149 共1983兲.
529 共1996兲. 198. G. Mengoli, G. Vidotto, and F. Furianetto, Makromol. Chem., 37, 203 共1970兲.
157. N. Anicet, A. Anna, C. Bourdillon, C. Demaille, J. Moiroux, and J.-M. Savéant, 199. G. S. Shapoval, J. Macromol. Sci., Chem., A17, 453 共1982兲.
Faraday Discuss., 116, 269 共2000兲. 200. H. Shirakawa, E. J. Louis, A. G. MacDiarmid, C. K. Chiang, and A. J. Heeger, J.
158. C. P. Andrieux, I. Gallardo, and J.-M. Savéant, J. Am. Chem. Soc., 111, 1620 Chem. Soc. Chem. Commun., 1977, 578 共1977兲.
共1989兲. 201. P. J. Nigrey, A. G. MacDiarmid, and A. J. Heeger, J. Chem. Soc. Chem. Commun.,
159. K. Daasbjerg, S. U. Pedersen, and H. Lund, in Measurements and Estimation of 1979, 594.
Redox Potentials of Organic Radicals in General Aspects of Free Radical Chem- 202. A. F. Diaz, K. K. Kanazawa, and G. P. Gardini, J. Chem. Soc. Chem. Commun.,
istry, Z. B. Alfassi, Editor, p. 385, John Wiley & Sons, New York 共1999兲. 1979, 635.
160. D. M. Wayner and D. Griller, J. Am. Chem. Soc., 107, 7764 共1985兲; B. A. Sim, P. 203. G. Tourillon and F. Garnier, J. Electroanal. Chem., 135, 173 共1982兲.
H. Milne, D. Griller, and D. D. Wayner, J. Am. Chem. Soc., 112, 6635 共1990兲. F. 204. A. F. Diaz and J. A. Logan, J. Electroanal. Chem., 111, 111 共1980兲.
Fontana, R. J. Kolt, Y. Huang, and D. D. M. Wayner, J. Org. Chem., 59, 4671 205. C. P. Andrieux, P. Audebert, P. Hapiot, and J.-M. Savéant, J. Am. Chem. Soc., 112,
共1994兲. 2439 共1990兲.
161. V. A. Benderskii, S. D. Babenko, Y. M. Zolotovitskii, A. G. Krivenko, and T. S. 206. P. Audebert, P. Hapiot, J.-M. Pernaut, and P. Garcia, J. Electroanal. Chem., 361,
Rudenko, J. Electroanal. Chem., 56, 325 共1974兲. V. A. Benderskii and A. G. 283 共1993兲.
Krivenko, Russ. Chem. Rev., 59, 1 共1990兲. 207. A. Smie, A. Synowczyk, J. Heinze, R. Alle, P. Tschuncky, G. Götz, and P. Bäuerle,
162. V. V. Konovalov, I. I. Bilkis, B. A. Selinavov, V. D. Sheingarts, and T. D. Tsvet- J. Electroanal. Chem., 452, 87 共1998兲; J. Heinze, H. John, M. Dietrich, and P.
kov, J. Chem. Soc., Perkin Trans. 2, 1993, 1707; P. Hapiot, V. V. Konovalov, and Tschuncky, Synth. Met., 119, 49 共2001兲.
J.-M. Savéant, J. Am. Chem. Soc., 117, 1428 共1995兲, J. Gonzalez, P. Hapiot, V. 208. M. A. Vorotyntsev and J. Heinze, Electrochim. Acta, 46, 3309 共2001兲.
Konovalov, and J.-M. Savéant, J. Am. Chem. Soc., 120, 10171 共1998兲. 209. E. M. Genies, G. Bidan, and A. F. Diaz, J. Electroanal. Chem., 149, 101 共1983兲.
163. R. Fuhlendorff, D. Occhialini, S. U. Pedersen, and H. Lund, Acta Chem. Scand., 210. T. Kobayashi, H. Yoneyama, and H. Tamura, J. Electroanal. Chem., 161, 419
43, 803 共1989兲; D. Occhialini, S. U. Pedersen, and H. Lund, Acta Chem. Scand., 共1984兲, 177, 281 共1984兲.
44, 715 共1990兲; D. Occhialini, J. S. Kristensen, S. U. Pedersen, and H. Lund, Acta 211. A. Kitani, J. Yano, and K. Sasaki, J. Electroanal. Chem., 209, 227 共1986兲.
Chem. Scand., 46, 474 共1992兲; D. Occhialini, K. Daasbjerg, and H. Lund, Acta 212. T. Kobayashi, H. Yoneyama, and H. Tamura, J. Electroanal. Chem., 161, 419
Chem. Scand., 47, 1100 共1993兲; H. Lund, K. Daasbjerg, D. Occhialini, and S. U. 共1984兲.
Pedersen, Russ. J. Electrochem., 31, 865 共1995兲. 213. E. Meggers, M. E. Michel-Beyerly, and B. Giese, J. Am. Chem. Soc., 120, 12950
164. S. U. Pedersen and T. Lund, Acta Chem. Scand., 45, 397 共1991兲. 共1998兲, E. Meggers, D. Kusch, M. Spichty, U. Wille, and B. Giese, Angew. Chem.
165. S. U. Pedersen, T. Lund, K. Daasbjerg, M. Pop, I. Fussing, and H. Lund, Acta Int. Ed. Engl., 37, 460 共1998兲.
Chem. Scand., 52, 657 共1998兲. 214. B. Hall, R. E. Holmlin, and J. K. Barton, Nature (London), 382, 731 共1996兲.
166. J. H. Wagenknecht and M. M. Baizer, J. Org. Chem., 31, 3885 共1966兲. 215. D. Ly, L. Sanii, and G. B. Schuster, J. Am. Chem. Soc., 121, 9400 共1999兲.
167. C. Amatore, G. Capobianco, G. Farnia, G. Sandona, J.-M- Savéant, M. G. Sev- 216. K. Fukui and K. Tanaka, Angew. Chem. Int. Ed. Engl., 37, 158 共1998兲.
erin, and E. Vianello, J. Am. Chem. Soc., 107, 1815 共1985兲; M. C. Arévalo, G. 217. H. Sugiyama and I. Saito, J. Am. Chem. Soc., 118, 7063 共1996兲.
Farnia, M. G. Severin, and E. Vianello, J. Electroanal. Chem., 220, 201 共1987兲. 218. H.-W. Fink and C. Schönenberger, Nature (London), 398, 407 共1999兲.
168. P. E. Iversen and H. Lund, Tetrahedron Lett., 1969, 3523. 219. M. A. Brett, A. M. O. Brett, and S. H. P. Serrano, J. Electroanal. Chem., 366, 225
169. R. C. Hallcher and M. M. Baizer, Liebigs Ann. Chem., 1977, 737. 共1994兲.
Journal of The Electrochemical Society, 149 共4兲 S21-S33 共2002兲 S33

220. M. Faraggi, F. Broitman, J. B. Trent, and M. H. Klapper, J. Phys. Chem., 100, 233. M. Troupel, Y. Rollin, S. Sibille, J.-P. Fauvarque, and J. Perichon, Chem. Res.
1475 共1996兲. Synop., 24, 26 共1980兲.
221. D. L. Croteau and V. A. Bohr, J. Biol. Chem., 272, 25409 共1997兲. 234. T. Itoh, S. Emoto, M. Kondo, H. Ohara, H. Tanaka, and S. Torii, Electrochim.
222. A. Heller, Faraday Discuss., 116, 1 共2000兲. Acta, 42, 2133 共1997兲.
223. L. Walder, in Organic Electrochemistry, 3rd ed., H. Lund and M. M. Baizer, 235. J.-i. Yoshida, T. Murata, and S. Isoe, Tetrahedron Lett., 27, 3373 共1986兲.
Editors, p. 809, Marcel Dekker, New York 共1991兲. 236. T. Shono, Y. Matsumura, S. Katoh, and N. Kise, Chem. Lett., 1985, 463.
224. J.-i. Yoshida and S. Suga, in Organic Electrochemistry, 4th ed., H. Lund and O. 237. J.-i. Yoshida, K. Muraki, H. Funahashi, and N. Kawabata, J. Org. Chem., 51, 3996
Hammerich, Editors, p. 765, Marcel Dekker, New York 共2001兲. 共1986兲.
225. W. J. Settineri and L. D. McKeever, in Technique of Electroorganic Synthesis, Part 238. J.-i. Yoshida, M. Watanabe, H. Toshioka, M. Imagawa, and S. Suga, in Novel
II, p. 397, John Wiley & Sons, New York 共1975兲. Trends in Electroorganic Synthesis, S. Torii, Editor, p. 99, Springer, Berlin 共1998兲;
226. G. Gritzner and J. Kuta, Pure Appl. Chem., 56, 461 共1984兲; G. Gritzner and J. J.-i. Yoshida, M. Watanabe, H. Toshioka, M. Imagawa, and S. Suga, J. Electroa-
Kuta, Electrochim. Acta, 29, 869 共1984兲. nal. Chem., 507, 55 共2001兲.
227. W. Eisenbach and H. Lemkuhl, Dechema-Monogr., 98, 269 共1985兲. 239. L. L. Bolt, Hydrocarbon Process, 44, 115 共1965兲.
228. K. M. Kadish, in Progress in Inorganic Chemistry, Vol. 34, S. J. Lippard, Editor, 240. M. M. Baizer, J. Electrochem. Soc., 111, 215 共1964兲.
p. 435, John Wiley & Sons, New York 共1986兲. 241. J. Chaussard, M. Troupel, Y. Robin, C. Jacob, and J. P. Jubasz, J. Appl. Electro-
229. D. Lexa and J.-M. Saveant, J. Am. Chem. Soc., 100, 3220 共1978兲; D. Lexa and chem., 19, 345 共1989兲.
J.-M. Saveant, Acc. Chem. Res., 16, 235 共1983兲. 242. A. Fontana, Chim. Nouv., 11, 1232 共1993兲.
230. R. Scheffold, Chimia, 39, 203 共1985兲, R. Scheffold, Nachr. Chem., Tech. Lab., 36, 243. M. M. Baizer, in Organic Electrochemistry, 3rd ed., H. Lund and M. M. Baizer,
261 共1988兲; S. Abrecht and R. Scheffold, Chimia, 39, 211 共1985兲. Editors, p. 1421, Marcel Dekker, New York 共1991兲.
231. S. Ozaki, H. Matsushita, and H. Ohmori, J. Chem. Soc., Perkin Trans. 1, 1993, 244. H. Pütter and H. Hannebaum, in New Directions in Organic Electrochemistry, A.
649. J. Fry and Y. Matsumura, Editors, PV 2000-15, p. 25, The Electrochemical Soci-
232. S. Torii, H. Tanaka, and K. Morisaki, Tetrahedron Lett., 26, 1655 共1985兲. ety Proceedings Series, Pennington, NJ 共2001兲.