(Ebook) Organic Electrochemistry by Ole Hammerich, Bernd

Speiser (eds.) ISBN 9781420084016, 1420084011 Pdf

Download

https://ebooknice.com/product/organic-electrochemistry-5290260

★★★★★
4.7 out of 5.0 (45 reviews )

DOWNLOAD PDF

ebooknice.com
 (Ebook) Organic Electrochemistry by Ole Hammerich, Bernd
Speiser (eds.) ISBN 9781420084016, 1420084011 Pdf Download

EBOOK

Available Formats

■ PDF eBook Study Guide Ebook

EXCLUSIVE 2025 EDUCATIONAL COLLECTION - LIMITED TIME

INSTANT DOWNLOAD VIEW LIBRARY

 We believe these products will be a great fit for you. Click
the link to download now, or visit ebooknice.com
to discover even more!

(Ebook) Organic Electrochemistry: Revised and Expanded by Ole

Hammerich (Editor); Bernd Speiser (Editor) ISBN 9780429141874,
9781420084016, 9781420084023, 0429141874, 1420084011, 142008402X

https://ebooknice.com/product/organic-electrochemistry-revised-and-
expanded-12195416

(Ebook) Biota Grow 2C gather 2C cook by Loucas, Jason; Viles,

James ISBN 9781459699816, 9781743365571, 9781925268492,
1459699815, 1743365578, 1925268497

https://ebooknice.com/product/biota-grow-2c-gather-2c-cook-6661374

(Ebook) Matematik 5000+ Kurs 2c Lärobok by Lena Alfredsson, Hans

Heikne, Sanna Bodemyr ISBN 9789127456600, 9127456609

https://ebooknice.com/product/matematik-5000-kurs-2c-larobok-23848312

(Ebook) Vagabond, Vol. 29 (29) by Inoue, Takehiko ISBN

9781421531489, 1421531488

https://ebooknice.com/product/vagabond-vol-29-29-37511002
(Ebook) SAT II Success MATH 1C and 2C 2002 (Peterson's SAT II
Success) by Peterson's ISBN 9780768906677, 0768906679

https://ebooknice.com/product/sat-ii-success-math-1c-and-2c-2002-peterson-
s-sat-ii-success-1722018

(Ebook) Master SAT II Math 1c and 2c 4th ed (Arco Master the SAT
Subject Test: Math Levels 1 & 2) by Arco ISBN 9780768923049,
0768923042

https://ebooknice.com/product/master-sat-ii-math-1c-and-2c-4th-ed-arco-
master-the-sat-subject-test-math-levels-1-2-2326094

(Ebook) Cambridge IGCSE and O Level History Workbook 2C - Depth

Study: the United States, 1919-41 2nd Edition by Benjamin
Harrison ISBN 9781398375147, 9781398375048, 1398375144,
1398375047
https://ebooknice.com/product/cambridge-igcse-and-o-level-history-
workbook-2c-depth-study-the-united-states-1919-41-2nd-edition-53538044

(Ebook) Boeing B-29 Superfortress ISBN 9780764302725, 0764302728

https://ebooknice.com/product/boeing-b-29-superfortress-1573658

(Ebook) Jahrbuch für Geschichte: Band 29 ISBN 9783112622223,

3112622227

https://ebooknice.com/product/jahrbuch-fur-geschichte-band-29-50958290
 FIFTH EDITION

ORGANIC
ELECTROCHEMISTRY
R E V I S E D A N D E X PA N D E D

© 2016 by Taylor & Francis Group, LLC

 FIFTH EDITION

ORGANIC
ELECTROCHEMISTRY
R E V I S E D A N D E X PA N D E D
EDITED BY

Ole Hammerich
University of Copenhagen, C o p e n h a g e n , D e n m a r k

Bernd Speiser
Universität Tübingen, Tü b i n g e n , G e r m a n y

Boca Raton London New York

CRC Press is an imprint of the

Taylor & Francis Group, an informa business

© 2016 by Taylor & Francis Group, LLC

 CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2016 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business

No claim to original U.S. Government works

Version Date: 20150731

International Standard Book Number-13: 978-1-4200-8402-3 (eBook - PDF)

This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been
made to publish reliable data and information, but the author and publisher cannot assume responsibility for the valid-
ity of all materials or the consequences of their use. The authors and publishers have attempted to trace the copyright
holders of all material reproduced in this publication and apologize to copyright holders if permission to publish in this
form has not been obtained. If any copyright material has not been acknowledged please write and let us know so we may
rectify in any future reprint.

Except as permitted under U.S. Copyright Law, no part of this book may be reprinted, reproduced, transmitted, or uti-
lized in any form by any electronic, mechanical, or other means, now known or hereafter invented, including photocopy-
ing, microfilming, and recording, or in any information storage or retrieval system, without written permission from the
publishers.

For permission to photocopy or use material electronically from this work, please access www.copyright.com (http://
www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC), 222 Rosewood Drive, Danvers, MA 01923,
978-750-8400. CCC is a not-for-profit organization that provides licenses and registration for a variety of users. For
organizations that have been granted a photocopy license by the CCC, a separate system of payment has been arranged.

Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for
identification and explanation without intent to infringe.
Visit the Taylor & Francis Web site at
http://www.taylorandfrancis.com
and the CRC Press Web site at
http://www.crcpress.com

© 2016 by Taylor & Francis Group, LLC

 Contents
Preface...............................................................................................................................................ix
Acknowledgments........................................................................................................................... xiii
Editors............................................................................................................................................... xv
Contributors....................................................................................................................................xvii

Section I  Fundamentals and Methods

Chapter 1 Basic Concepts.............................................................................................................. 3

Christian Amatore

Chapter 2 Techniques for Studies of Electrochemical Reactions in Solution..............................97

Ole Hammerich and Bernd Speiser

Chapter 3 In Situ Spectroelectrochemistry of Organic Compounds......................................... 169

Peter Rapta, Evgenia Dmitrieva, Alexey A. Popov, and Lothar Dunsch

Chapter 4 Surface Techniques................................................................................................... 191

Mohamed M. Chehimi and Jean Pinson

Chapter 5 Application of Digital Simulation............................................................................. 205

Bernd Speiser

Chapter 6 Theoretical Calculation of Reduction Potentials....................................................... 229

Junming Ho, Michelle L. Coote, Christopher J. Cramer, and Donald G. Truhlar

Section II  General Preparative Aspects

Chapter 7 Preparative Electrolysis on the Laboratory Scale..................................................... 263

Jakob Jörissen and Bernd Speiser

Chapter 8 Application of Ionic Liquids, Emulsions, Sonication, and Microwave Assistance...... 331
John D. Watkins and Frank Marken

© 2016 by Taylor & Francis Group, LLC

 vi Contents

Chapter 9 Combinatorial Electrochemistry and Miniaturization.............................................. 345

Kevin D. Moeller

Chapter 10 Relations between Micro- and Macrophenomena..................................................... 371

Christian Amatore

Section III Electron Transfers and Concerted Processes

Chapter 11 Influence of Molecular and Medium Effects on Two-Electron Processes................ 395

Kevin Lam and William E. Geiger

Chapter 12 Electrochemically Driven Supramolecular Devices................................................. 433

Paola Ceroni, Alberto Credi, and Margherita Venturi

Chapter 13 Proton-Coupled Electron Transfers........................................................................... 481

Cyrille Costentin, Marc Robert, and Jean-Michel Savéant

Chapter 14 Dissociative Electron Transfers................................................................................. 511

Cyrille Costentin, Marc Robert, and Jean-Michel Savéant

Chapter 15 Electron Transfer–Catalyzed Reactions.................................................................... 531

Kazuhiro Chiba and Yohei Okada

Section IV Organic Electrochemical Reaction Types

Chapter 16 Cleavages and Deprotections.................................................................................... 559

Ole Hammerich

Chapter 17 Reductive Coupling................................................................................................... 621

James H.P. Utley, R. Daniel Little, and Merete Folmer Nielsen

Chapter 18 Oxidative Coupling................................................................................................... 705

Hans J. Schäfer

Chapter 19 Oxidative Substitution and Addition Reactions........................................................ 775

Ole Hammerich and James H.P. Utley

Chapter 20 Fluorination...............................................................................................................807
Toshio Fuchigami and Shinsuke Inagi

© 2016 by Taylor & Francis Group, LLC

 Contents vii

Section V Electrochemical Conversions of Organic Compounds

Chapter 21 Electrochemistry of Fullerenes, Derivatives, and Related Compounds.................... 829
Frederic Melin, Lourdes E. Echegoyen, and Luis Echegoyen

Chapter 22 Aliphatic and Aromatic Hydrocarbons: Reduction................................................... 861

Jürgen Heinze

Chapter 23 Oxidation of Hydrocarbons....................................................................................... 891

Ole Hammerich

Chapter 24 Activation of the Carbon–Halogen Bond.................................................................. 917

Armando Gennaro, Abdirisak Ahmed Isse, and Patrizia Romana Mussini

Chapter 25 Aliphatic and Aromatic Halides: Conversions.......................................................... 941

Dennis G. Peters

Chapter 26 Oxygen-Containing Compounds: Alcohols, Ethers, and Phenols............................ 981

Robert Francke, Thomas Quell, Anton Wiebe, and Siegfried R. Waldvogel

Chapter 27 Sulfur-, Selenium-, and Tellurium-Containing Compounds................................... 1035

Richard S. Glass

Chapter 28 Aliphatic Nitrogen–Containing Compounds: Amines, Amino Alcohols,

and Amino Acids.................................................................................................... 1103
Osamu Onomura

Chapter 29 Aromatic Nitrogen–Containing Compounds...........................................................1121

Jan S. Jaworski

Chapter 30 Reduction of Nitro Compounds and Related Substrates..........................................1149

Ole Hammerich

Chapter 31 Reduction of Aldehydes, Ketones, and Azomethines............................................. 1201

Jiří Ludvík

Chapter 32 Reductions of Carboxylic Acids and Derivatives.................................................... 1249

Rolf Breinbauer and Martin Peters

Chapter 33 Oxidation of Carboxylic Acids and Derivatives..................................................... 1267

Hideo Tanaka, Manabu Kuroboshi, and Sigeru Torii

© 2016 by Taylor & Francis Group, LLC

 viii Contents

Chapter 34 Heterocyclic Compounds........................................................................................ 1309

Fructuoso Barba and Belen Batanero

Chapter 35 Organoelemental Compounds................................................................................. 1357

Jun-ichi Yoshida, Toshiki Nokami, and Seiji Suga

Chapter 36 Organometallic Compounds as Tools in Organic Electrosynthesis........................ 1393

Anny Jutand

Section VI  Stereochemical and Biological Aspects

Chapter 37 Electrosynthesis of Bioactive Materials.................................................................. 1435
Randi K. Gbur and R. Daniel Little

Chapter 38 Stereochemistry of Organic Electrode Processes................................................... 1461

Toshio Fuchigami and Shinsuke Inagi

Chapter 39 Electroenzymatic Synthesis.....................................................................................1511

Christina Kohlmann and Stephan Lütz

Chapter 40 Electrochemical Modeling of Biological Processes................................................ 1543

Richard D. Webster

Section VII  Surface Confined Systems

Chapter 41 Electrochemistry of Conducting Polymers............................................................. 1571
Jürgen Heinze

Chapter 42 Surface-Bound and Immobilized Molecules.......................................................... 1605

Jean Pinson

Section VIII  Special Applications

Chapter 43 Electrogenerated Bases and Nucleophiles............................................................... 1625
James H.P. Utley, Merete Folmer Nielsen, and Peter B. Wyatt

Chapter 44 Electrocatalytic Hydrogenation............................................................................... 1657

Jean Lessard

Index............................................................................................................................................. 1673

© 2016 by Taylor & Francis Group, LLC

 Preface
Organic electrochemistry is concerned with the reduction and oxidation of organic molecules at
electrodes. Although it is now more than 200 years ago that the so-called Volta pile was discov-
ered, it was not until 1830–1850 that investigations of organic electrochemical processes, pioneered
by Faraday and Kolbe, were established as a research area in their own right. Toward the end of
the nineteenth century, investigators such as Tafel and Haber made significant contributions to the
present knowledge of organic electrode processes. Haber, for instance, in his now famous paper
on the reduction of nitrobenzene (F. Haber, Z. Elektrochem. 1898, 4, 506) recognized the signifi-
cance of the electrode potential in the following words: “Oxydations- und Reduktionsprozesse hän-
gen in erster Linie von dem Potential der Elektrode ab, an welcher sie ablaufen, und Stromdichte,
Stromdauer und Elektrodenmaterial sind nur insofern bedeutsam, als sie das Elektrodenpotential
und seine Änderungen im Gang der Elektrolyse bestimmen.” (“Oxidation and reduction processes
primarily depend on the potential of the electrode at which they proceed, and current density, cur-
rent duration, and electrode material are only important insofar as they determine the electrode
potential and its changes during the electrolysis.”) The application of electrolysis as a means of
preparing organic compounds continued in the first half of the twentieth century. This development
took place along with the development of new electrochemical techniques for the study of electrode
processes, for instance, polarography at the dropping mercury electrode introduced by Heyrovsky
in the early 1920s. Other important contributions were due to Lingane, Kolthoff, Laitinen, and
Delahay. Later, Hickling’s potentiostat (A. Hickling, Trans. Faraday Soc. 1942, 38, 27) as an exper-
imental tool to control experiments led into the computerization era.
Most of the work reported before World War II was carried out in aqueous electrolyte solu-
tions. This situation changed after the war, and since the mid-1950s, the attention has been focused
mostly on the application of nonaqueous solvents. This has allowed for the detection of the primary
intermediates, typically radical anions and radical cations, and for the study of their reactions. The
theoretical foundations for the analysis of kinetics and mechanisms by, for instance, cyclic voltam-
metry and related techniques were mostly published in the 1960s and 1970s. The application of such
techniques has resulted in a steadily increasing understanding of the kinetics and mechanisms of
organic electrochemical processes.
Facing the fact that thousands of organic electrochemical processes are now known, it is striking
that most often the only electrochemical reaction to be mentioned in a typical organic chemistry
textbook is the oxidation of an organic carboxylic acid R-COOH to the corresponding dimeric
alkane R-R reported by Kolbe as early as 1849. Also, it is often overlooked that reductions by met-
als involving radical anions as intermediates are intimately related to cathodic reductions. And
most frequently, radical cations are not mentioned at all, except, of course, in the context of mass
spectrometry! This problem, that organic electrochemistry has had difficulties in penetrating into
the organic chemistry curriculum, was pointed out already in the preface to the first edition of this
book. Unfortunately, not much has changed in the more than 40 years that have elapsed between
that edition and this fifth edition.
The knowledge of organic electrochemistry had in the 1960s and the early 1970s matured to the
point where the time was ripe for the first edition of Organic Electrochemistry (M.M. Baizer, ed.,
Organic Electrochemistry, Marcel Dekker: New York, 1973). The editor was Manual M. Baizer,
well known for his contributions to preparative organic electrochemistry, first of all the develop-
ment of the electrohydrodimerization of acrylonitrile into a highly successful industrial process for
the manufacture of adiponitrile. Baizer set the standards for the book that was organized to include
chapters both on the electrochemical reduction and oxidation of specific classes of compounds and

ix

© 2016 by Taylor & Francis Group, LLC

 x Preface

on specific types of electrode processes. This approach obviously led to some overlap, a problem that
Baizer touched upon in the following words: “It has become routine, at least for reviewers, to point
out that in a multi-authored book there is overlap of material, non-uniformity of style, repetition etc.
This book was not hastily assembled, and there was adequate time to achieve uniformity if that had
been desired. But the material was deliberately organized so that a given segment might appear in
two or more contexts and, further, where unanimity of opinion does not exist, more than one current
viewpoint might be expressed.” The same basic philosophy was followed in the organization of the
second (Baizer, M.M., Lund, H., eds., Organic Electrochemistry, Marcel Dekker: New York, 1983),
third (Lund, H., Baizer, M.M., eds., Organic Electrochemistry, Marcel Dekker: New York, 1991),
fourth (Lund, H., Hammerich, O., eds., Organic Electrochemistry, Marcel Dekker: New York, 2001)
editions, and now for this fifth edition. Owing to this intentional overlap between chapters, the reader
is encouraged to use the index to find details, in addition to those found in a given chapter, of the
electrochemistry of a specific compound or a class of compounds. Also, some formal variations that
reflect common usage by different authors have not been brought into line, for example, the use of “e”
or “e −” for the electron or the nomenclature of electrochemical mechanisms (“ECE” vs. “eCe,” etc.).
The progress in organic electrochemistry that has taken place since the appearance of the fourth
edition is reflected by the organization of this edition. Organic electrochemical reactions are rather
complex with electron transfers and transport processes interwoven with bond breaking and forming
reaction steps. As a consequence, different perspectives have developed over the years and organic
electrochemistry may be discussed following different lines of thought. Moreover, organic electro-
chemical reactions are often integrated into more complicated synthetic strategies and advanced
chemical reasoning or are applied to complex materials and structures. Consequently, it was decided
to present the field as follows. After an introduction of some basic and technical aspects, the reac-
tion step that distinguishes organic electrochemistry from classical organic reactions, the electron
transfer to and from organic molecules, is described and its most important variants are presented.
Second, the importance of electron transfers for the initiation of various organic electrochemical
reaction types (follow-up reactions) is emphasized. Third, the electrochemical transformations of
organic compounds are systematically presented according to the type of starting materials. Finally,
cases where organic electrochemistry forms an integral part in a wider context of chemical research
(e.g., in biological or materials science) are discussed.
In comparison with the fourth edition, the following major changes have been made to this
edition:
Sixteen new chapters have been included. These are:

• Chapter 3: In Situ Spectroelectrochemistry of Organic Compounds by Peter Rapta, Evgenia

Dmitrieva, Alexey A. Popov, and Lothar Dunsch
• Chapter 4: Surface Techniques by Mohamed M. Chehimi, and Jean Pinson
• Chapter 5: The Application of Digital Simulation by Bernd Speiser
• Chapter 6: Theoretical Calculation of Reduction Potentials by Junming Ho, Michelle L.
Coote, Christopher J. Cramer, and Donald G. Truhlar
• Chapter 8: The Application of Ionic Liquids, Emulsions, Sonication, and Microwave
Assistance by John D. Watkins and Frank Marken
• Chapter 9: Combinatorial Electrochemistry and Miniaturization by Kevin D. Moeller
• Chapter 11: Influence of Molecular and Medium Effects on Two-Electron Processes by
Kevin Lam and William E. Geiger
• Chapter 12: Electrochemically Driven Supramolecular Devices by Paola Ceroni, Alberto
Credi, and Margherita Venturi
• Chapter 13 and 14: Proton-Coupled Electron Transfers and Dissociative Electron Transfers
by Cyrille Costentin, Marc Robert, and Jean-Michel Savéant
• Chapter 15: Electron Transfer Catalyzed Reactions by Kazuhiro Chiba and Yohei Okada

© 2016 by Taylor & Francis Group, LLC

 Preface xi

• Chapter 24: Activation of the Carbon-Halogen Bond by Armando Gennaro, Abdirisak

Ahmed Isse, and Patrizia Romana Mussini
• Chapter 36: Organometallic Compounds as Tools in Organic Electrosynthesis by Anny
Jutand
• Chapter 40: Electrochemical Modeling of Biological Processes by Richard D. Webster
• Chapter 42: Surface-Bound and Immobilized Molecules by Jean Pinson
• Chapter 44: Electrocatalytic Hydrogenation by Jean Lessard

Approximately one-fourth of the previous chapters have been rewritten by new authors:

• Chapter 7: Preparative Electrolysis on the Laboratory Scale by Jakob Jörissen and Bernd
Speiser
• Chapter 16: Cleavages and Deprotections by Ole Hammerich
• Chapter 26: Oxygen Containing Compounds: Alcohols, Ethers, and Phenols by Robert
Francke, Thomas Quell, Anton Wiebe, and Siegfried R. Waldvogel
• Chapter 27: Sulfur, Selenium, and Tellurium Containing Compounds by Richard S. Glass
• Chapter 30: Reduction of Nitro Compounds and Related Substrates by Ole Hammerich
• Chapter 31: Reduction of Aldehydes, Ketones, and Azomethines by Jiri Ludvik
• Chapter 32: Reduction of Carboxylic Acids and Derivatives by Rolf Breinbauer and Martin
Peters
• Chapter 34: Heterocyclic Compounds by Fructuoso Barba and Belen Batanero
• Chapter 39: Electroenzymatic Synthesis by Christina Kohlmann and Stephan Lütz

All other chapters have been thoroughly revised or updated where needed, in some cases in coop-
eration with new coauthors.
The following four chapters have been omitted:

• Old Chapter 4: Comparison Between Electrochemical Reactions and Chemical Oxidations

and Reductions
• Old Chapter 28: Amalgam and Related Reductions
• Old Chapter 29: Electrogenerated Reagents
• Old Chapter 31: Industrial Electroorganic Chemistry

Thus, in a sense, this is a new book and not just a conservative update to the previous edition.
Altogether this book encompasses 44 chapters written by 66 authors.
In most cases, we have encouraged authors to avoid back references to the fourth edition.
However, this was not always possible, nor desirable. The text of some chapters in the fourth edition
is still authoritative and not much could be added (see, e.g., the appendices on solvents and support-
ing electrolytes in Chapter 7).
Many of the authors of the fourth and previous editions have now retired. Fortunately, new
authors have willingly accepted to carry the torch on to this new edition. Sadly, one of these new
authors, Lothar Dunsch, passed away in late 2013. This was a great loss to the electrochemical com-
munity, and he will be remembered as one of the leading figures in the development and application
of spectroelectrochemistry.

Ole Hammerich
Bernd Speiser

© 2016 by Taylor & Francis Group, LLC

 Acknowledgments
The editors thank all the authors for the enthusiasm with which they have undertaken the enormous
task of making this fifth edition possible. We have strived to maintain the basic philosophy and
not least the high standards of the previous editions to make this a worthy fifth edition of the well-
known “Baizer.” Hopefully, we have succeeded.
We acknowledge the help of several people who have contributed “behind the scenes” in
some way or the other. Klaus-Michael Mangold (Frankfurt/Main, Germany), Susanne Hempel
(Tübingen, Germany), and Tatiana V. Magdesieva (Moscow, Russia) helped with locating or citing
some unusual references. Practically, each and every manuscript file (often in a multitude of ver-
sions) went through the hands (and across the fingertips) of Britta Rochier (Tübingen, Germany),
who almost always found a way to cope with the astonishingly variable word processing software
in use around the world.
Finally, we thank the staff at Taylor & Francis Group, Barbara Glunn, Kari A. Budyk, and
Jennifer Derima, for their patience with our inquiries while we were collecting the manuscripts
from the authors.

xiii

© 2016 by Taylor & Francis Group, LLC

 Editors
Ole Hammerich is an associate professor in the Department of Chemistry, University of
Copenhagen, Denmark, where he has taught since 1975. Dr. Hammerich’s research interests include
kinetics and mechanisms of organic radical ion reactions, charge-transfer complexes, and elec-
tropolymerization. He is author or coauthor of more than 110 articles, papers, and book chapters
and was, together with Henning Lund, the editor of the fourth edition of Organic Electrochemistry.
Together with Jens Ulstrup, he was the editor of Bioinorganic Electrochemistry. Dr. Hammerich
has served as the national secretary for Denmark and as the chairman of the molecular electrochem-
istry division in the International Society of Electrochemistry and he is a member of the Danish
Electrochemical Society and the Electrochemical Society. He earned his PhD (1974) from the
University of Copenhagen, Denmark.
Bernd Speiser is an außerplanmäßiger professor in the Institut für Organische Chemie, Universität
Tübingen, Germany. He received his doctoral degree in Tübingen in 1981 and finished his habili-
tation in 1990. He was a Heisenberg fellow of the Deutsche Forschungsgemeinschaft in the years
1992–1996. He teaches courses in organic chemistry and molecular electrochemistry. His research
is focused on the elucidation of reaction mechanisms of organic, organometallic, and inorganic
compounds with experimental methods and computer simulation. This includes the study of multi-
electron transfers, transport properties, redox-active nanoparticles, and combinatorial electro-
chemistry. He has published more than 140 full papers, communications, and book chapters. He
was the founding chair of Division 6 (molecular electrochemistry) in the International Society of
Electrochemistry and is a member of the Electrochemical Society, the International Society of
Electrochemistry, the Society of Electroanalytical Chemistry, the Gesellschaft Deutscher Chemiker
(GDCh), and DECHEMA Gesellschaft für chemische Technik und Biotechnologie.

xv

© 2016 by Taylor & Francis Group, LLC

 Contributors
Christian Amatore Michelle L. Coote
Ecole Normale Supérieure ARC Centre of Excellence for
Department of Chemistry Electromaterials Science
(ENS-CNRS-UPMC) Research School of Chemistry
PSL Research Univerisity Australian National University
Sorbonne Universités Canberra, Australian Capital Territory,
Paris, France Australia

Fructuoso Barba Cyrille Costentin

Department of Organic Chemistry Laboratoire d’Electrochimie Moléculaire,
University of Alcala UMR CNRS 7591
Madrid, Spain Université Paris Diderot
Sorbonne Paris Cité
Paris, France
Belen Batanero
Department of Organic Chemistry Christopher J. Cramer
University of Alcala Department of Chemistry, Chemical Theory
Madrid, Spain Center, and Supercomputing Institute
University of Minnesota
Rolf Breinbauer Minneapolis, Minnesota
Institute of Organic Chemistry
Graz University of Technology Alberto Credi
Graz, Austria Dipartimento di Chimica “G. Ciamician”
Alma Mater Studiorum
Paola Ceroni Università di Bologna
Dipartimento di Chimica “G. Ciamician” Bologna, Italy
Alma Mater Studiorum
Università di Bologna Evgenia Dmitrieva
Bologna, Italy Department of Electrochemistry and
Conducting Polymers
Center of Spectroelectrochemistry
Mohamed M. Chehimi Leibniz Institute for Solid State and Materials
Université Paris Diderot Research
Sorbonne Paris Cité, ITODYS, UMR 7086 Dresden, Germany
CNRS
Paris, France Lothar Dunsch (deceased)
Department of Electrochemistry and
Kazuhiro Chiba Conducting Polymers
Department of Applied Biological Chemistry Center of Spectroelectrochemistry
Tokyo University of Agriculture and Leibniz Institute for Solid State and Materials
Technology Research
Tokyo, Japan Dresden, Germany

xvii

© 2016 by Taylor & Francis Group, LLC

 xviii Contributors

Lourdes E. Echegoyen Junming Ho

Department of Chemistry Institute of High Performance Computing
University of Texas at El Paso Singapore
El Paso, Texas
Shinsuke Inagi
Luis Echegoyen Department of Electronic Chemistry
Department of Chemistry Tokyo Institute of Technology
University of Texas at El Paso Yokohama, Japan
El Paso, Texas
Abdirisak Ahmed Isse
Robert Francke Dipartimento di Scienze Chimiche
Department of Chemistry Università degli Studi di Padova
University of Rostock Padova, Italy
Rostock, Germany
Jan S. Jaworski
Toshio Fuchigami Faculty of Chemistry
Department of Electronic Chemistry University of Warsaw
Tokyo Institute of Technology Warszawa, Poland
Yokohama, Japan
Jakob Jörissen
Randi K. Gbur Lehrstuhl für Technische Chemie (Chemische
Department of Chemistry and Biochemistry Prozessentwicklung)
University of California, Santa Barbara Technische Universität Dortmund
Santa Barbara, California Dortmund, Germany

William E. Geiger Anny Jutand

University of Vermont Département de Chimie
Burlington, Vermont Ecole Normale Supérieure
Paris, France
Armando Gennaro
Christina Kohlmann
Dipartimento di Scienze Chimiche
BASF Personal Care and Nutrition GmbH
Università degli Studi di Padova
Düsseldorf, Germany
Padova, Italy
Manabu Kuroboshi
Richard S. Glass School of Natural Science and Technology
Department of Chemistry and Biochemistry Okayama University
The University of Arizona Okayama, Japan
Tucson, Arizona
Kevin Lam
Ole Hammerich School of Science and Technology
Department of Chemistry Nazarbayev University
University of Copenhagen Astana, Kazakhstan
Copenhagen, Denmark
Jean Lessard
Jürgen Heinze Laboratoire de Chimie et Électrochmie
Institut für Physikalische Chemie Organiques
Freiburger Materialforschungszentrum Département de Chimie
Universität Freiburg Université de Sherbrooke
Freiburg, Germany Sherbrooke, Québec, Canada

© 2016 by Taylor & Francis Group, LLC

 Contributors xix

R. Daniel Little Osamu Onomura

Department of Chemistry and Biochemistry Nagasaki University
University of California, Santa Barbara Nagasaki, Japan
Santa Barbara, California

Jiří Ludvík Dennis G. Peters

Department of Molecular Electrochemistry Department of Chemistry
J. Heyrovský Institute of Physical Chemistry Indiana University
Academy of Sciences of the Czech Republic Bloomington, Indiana
Prague, Czech Republic
Martin Peters
Stephan Lütz Institute of Organic Chemistry
Global Discovery Chemistry Graz University of Technology
Novartis Pharma AG Graz, Austria
Basel, Switzerland

Frank Marken Jean Pinson

Department of Chemistry Université Paris Diderot
University of Bath Sorbonne Paris Cité, ITODYS, UMR 7086
Bath, United Kingdom CNRS
Paris, France
Frederic Melin
Laboratoire de Bioélectrochimie
et Spectroscopie Alexey A. Popov
Université de Strasbourg Department of Electrochemistry and
Strasbourg, France Conducting Polymers
Center of Spectroelectrochemistry
Kevin D. Moeller Leibniz Institute for Solid State and Materials
Department of Chemistry Research
Washington University in St. Louis Dresden, Germany
St. Louis, Missouri
Thomas Quell
Patrizia Romana Mussini
Department of Organic Chemistry
Dipartimento di Chimica
Johannes Gutenberg University
Università degli Studi di Milano
Mainz, Germany
Milan, Italy

Merete Folmer Nielsen Peter Rapta

The Danish Emergency Management Agency Institute of Physical Chemistry and Chemical
Birkerød, Denmark Physics
Slovak University of Technology Bratislava
Toshiki Nokami Bratislava, Slovak Republic
Department of Chemistry and Biotechnology
Tottori University
Tottori, Japan Marc Robert
Laboratoire d’Electrochimie Moléculaire,
Yohei Okada UMR CNRS 7591
Graduate School of Biomedical Sciences Université Paris Diderot
Tokyo University of Agriculture and Technology Sorbonne Paris Cité
Tokyo, Japan Paris, France

© 2016 by Taylor & Francis Group, LLC

 xx Contributors

Jean-Michel Savéant Margherita Venturi

Laboratoire d’Electrochimie Moléculaire, Dipartimento di Chimica “G. Ciamician”
UMR CNRS 7591 Alma Mater Studiorum
Université Paris Diderot Università di Bologna
Sorbonne Paris Cité Bologna, Italy
Paris, France
Siegfried R. Waldvogel
Hans J. Schäfer Department of Organic Chemistry
Organisch-Chemisches Institut Johannes Gutenberg University
Westfälische Wilhelms-Universität Mainz, Germany
Münster, Germany
John D. Watkins
Bernd Speiser
Department of Chemistry
Institut für Organische Chemie
University of Bath
Universität Tübingen
Bath, United Kingdom
Tübingen, Germany

Seiji Suga Richard D. Webster

Division of Applied Chemistry Division of Chemistry and Biological
Graduate School of Natural Science and Chemistry
Technology School of Physical and Mathematical
Okayama University Sciences
Okayama, Japan Nanyang Technological University
Singapore, Singapore
Hideo Tanaka
School of Natural Science and Technology Anton Wiebe
Okayama University Department of Organic Chemistry
Okayama, Japan Johannes Gutenberg University
Mainz, Germany
Sigeru Torii
The Institute of Creative Chemistry Co., Ltd.
Peter B. Wyatt
Okayama-City, Japan
School of Biological and Chemical
Donald G. Truhlar Sciences
Department of Chemistry, Chemical Theory Queen Mary University of London
Center, and Supercomputing Institute London, United Kingdom
University of Minnesota
Minneapolis, Minnesota Jun-ichi Yoshida
Department of Synthetic Chemistry and
James H.P. Utley Biological Chemistry
School of Biological and Chemical Sciences Graduate School of Engineering
Queen Mary University of London Kyoto University
London, United Kingdom Kyoto, Japan

© 2016 by Taylor & Francis Group, LLC

 Section I
Fundamentals and Methods

© 2016 by Taylor & Francis Group, LLC

 1 Basic Concepts
Christian Amatore

Contents
I. Introduction............................................................................................................................... 4
II. Fundamental Aspects of Electron Transfer Reactions.............................................................. 6
A. Oxidation–Reduction Reactions versus Electron Transfer Reactions in Organic
Chemistry and Electrochemistry�������������������������������������������������������������������������������������� 6
1. Oxidation–Reduction versus Electron Transfer Reactions......................................... 6
2. Outer Sphere and Inner Sphere Electron Transfers.................................................... 8
B. Standard Potentials: What They Mean and What They Do Not Mean........................... 11
1. Standard Potentials................................................................................................... 11
2. Reference Electrodes and Liquid Junction Potentials............................................... 12
3. Standard Reduction Potentials versus Ionization Potentials or Electron
Affinities.................................................................................................................14
4. Comparison or Extrapolation between Solvents....................................................... 16
5. Formal Reduction Potentials..................................................................................... 17
6. Relationships between Thermodynamic Driving Force ΔE 0 and Feasibility
of an Electron Transfer Reaction�����������������������������������������������������������������������������20
C. Mechanism and Theory of Outer Sphere Electron Transfer Reactions........................... 22
1. Diffusion Limitation in Electron Transfer Reactions............................................... 22
2. Basic Features of Electron Transfer in Solution.......................................................26
3. Role of the Solvent: The Outer Shell Reorganization Energy.................................. 31
4. Physical Meaning of the Reorganization Energy and of Energy Diagrams............. 33
5. Energies and Free Energies in Electron Transfer Theories...................................... 35
6. Quadratic Free Energy Relationships....................................................................... 36
7. Cross-Relationships: Evaluation of Rate Constants from Isotopic Rate Constants......38
8. Experimental Illustrations........................................................................................ 39
III. Fundamental Aspects of Electrode Phenomena...................................................................... 42
A. Monitoring a Half-Reaction: The Electrochemical Cell.................................................. 42
1. Monitoring a Half-Reaction...................................................................................... 42
2. Electrochemical Cell.................................................................................................44
3. Resistive Effects and Ohmic Drop: The Supporting Electrolyte–Solvent
System....................................................................................................................... 45
4. Electrode/Solution Interfacial Region.......................................................................46
B. General Overview of an Electrode Reaction................................................................... 47
C. Kinetics of Heterogeneous Electron Transfers................................................................ 48
1. Mechanism and Theory of Outer Sphere Electron Transfers at Electrodes............. 48
2. Transfer Coefficient α............................................................................................... 52
3. Reversible and Irreversible Electron Transfers: Their Role in the Meaning
of Oxidation or Reduction Potentials����������������������������������������������������������������������� 53
D. Adsorption Phenomena.................................................................................................... 55

© 2016 by Taylor & Francis Group, LLC

 4 Organic Electrochemistry

E.
Coupled Chemical Reactions........................................................................................... 55
1. Electrochemical versus Homogeneous Chemical Reactivities................................. 55
2. Chemical Reversibility and Irreversibility: Their Role in the Meaning
of Oxidation or Reduction Potentials����������������������������������������������������������������������� 57
3. Classification of Coupled Chemical Reactions......................................................... 59
4. Electrochemical Reaction Mechanisms and the Principle of Microscopic
Reversibility..............................................................................................................64
IV. Mass Transfer in Electrochemistry.......................................................................................... 65
A. Fundamental Aspects of Mass Transfer Processes.......................................................... 65
1. Physical Processes of Mass Transfer: Fick’s First Law............................................66
2. Relationships between the Electrochemical Current and Mass Transfers................ 68
3. Microscopic Origin of the Diffusion Coefficient: Mass Transfer Rates and
Diffusion Layer Thickness....................................................................................... 70
4. Electrochemical Homogeneous Kinetics: Fick’s Second Law.................................. 72
5. Dimensionless Formulation of Electrochemical Equations...................................... 74
B. Steady-State Electrochemical Methods: Half-Wave Potential E1/2.................................. 78
1. Pure Electron Transfer Mechanisms......................................................................... 78
2. Mechanism Involving a Follow-Up Reaction: EC Mechanisms............................... 81
3. Chemical Kinetics from Half-Wave Potentials: Determination of Rate
Constants and Reaction Orders��������������������������������������������������������������������������������84
C. Transient Electrochemical Methods................................................................................ 87
1. Introduction: Time Hysteresis in Current Reversal Techniques............................... 87
2. Transient Electrochemical Methods and Chemical Kinetics...................................90
Acknowledgments.............................................................................................................................92
References.........................................................................................................................................92

A te convien tenere altro viaggio …

Chè questa bestia, per la qual tu gride,
Non lascia altrui pasar per la sua via,
Ma tanto lo impedisce, che l’uccide…
Dante
Divina Commedia

I. Introduction
Our objective in this chapter is to familiarize organic chemists with fundamental electrochemical
concepts that support several aspects of organic electrochemistry elaborated in this book, as well as
many important features of electron transfer reactions. In fact, although the term electrochemistry
evokes for most readers the idea of chemistry at electrodes, in our opinion, electron transfer chem-
istry constitutes a better definition when organic or organometallic electrochemistry is concerned.
This is particularly obvious when one thinks of an electrode as a macrosized molecule whose abil-
ity to provide or accept electrons is virtually infinite (versus a one-shot molecular redox species)
and may be precisely adjusted by fine-tuning of the electrode potential. Similarly, electrochemical
reactions involving specific interactions with the electrode material are no more than the analogs
of inner sphere, ion-pairing, or complexation reactions. Thus, in many respects, electrochemical
reactions do not differ basically from their homogeneous counterparts except for the topology: an
electrode is a 2D structure placed in a 3D volume, while molecular redox species are generally dis-
persed in the solution. This similarity is even more true insofar as it concerns the chemical reactiv-
ity of electrogenerated intermediates, since they evolve under conditions that a priori do not differ
from those considered in homogeneous chemistry. Indeed, the extraordinarily large electric fields
(of magnitude comparable to those at the origin of storm lightning) drop to negligible values within

© 2016 by Taylor & Francis Group, LLC

 Basic Concepts 5

a few angstroms of the electrode surface, in contradiction to generally held ideas. Thus, as soon as
molecules have moved over a few molecular diameters from the electrode surface, they probe no
special electrical effects associated with their electrochemical origin. This is an important point,
although not well recognized or publicized, since it permits an easy transposition of electrochemical
results to homogeneous situations or vice versa.
Yet there are specific particularities of chemistry at electrodes. They arise from the fact that
electrodes both supply and accept electrons to and from molecules dissolved in a solution. This
has two important consequences dealing with mass transfer (i.e., transfer of the reagents from the
homogeneous volumic space and to the heterogeneous 2D surface) and with current transport across
the solution.
Transport of the current through the solution requires that rather conductive media be used, at
least when high currents are considered. The ensuing necessity for an inert electrolyte is an obvi-
ous disadvantage of electrochemical methods, although in our opinion, it is fully compensated by
the extraordinary advantage of a precise adjustment of the driving force via the electrode potential.
Mass transfer from a volumic homogeneous region, the bulk solution, to a 2D surface results in
a spatial structuring of solutions in the close vicinity of the electrode surface. Although such effects
are not specific to electrochemistry,* they may be thought of, at first, as additional difficulties to
cope with in electrochemistry. However, these spatial structurings may be used with considerable
advantage to control the chemical route followed by a given intermediate and force it into a pathway
that would never be followed under homogeneous conditions. Indeed, this is used in most electro-
chemical reactions, especially in indirect reductions or oxidations, in which the proper choice of the
electron transfer mediator or of the electrogenerated reagent precursor is crucial to the success of a
particular reaction.
From our experience, the largest difficulty (or intellectual activation barrier) that homogeneous
chemists encounter in trying to deal with the electrochemical literature is directly related to elec-
trochemical jargon rather than to fundamental concepts. Although electrochemistry was born as a
synthetic method (by Kolbe, Haber, and Fichter, among others), most electrochemical textbooks use
an analytic approach to these fundamental concepts. As a result, mathematical formulations and
jargon invade most of the presentations, which often results in an effect similar to the caveat at the
entrance of Dante’s Inferno:

Per me si va nella città dolente,

Per me si va nell’ eterno dolore
Per me si va tra la perduta gente …
Lasciate ogni speranza, voi ch’ entrate.
Dante Alighieri
Divina Commedia

Our point is not to criticize these necessary and worthwhile approaches that give to electrochem-
istry its ability to interpret and rationalize on a quantitative basis a large number of experimental
facts that extend far beyond strictly electrochemical domains. Most of our published work (as well
as the later sections of this chapter) advocates our belief in the usefulness of these physicomath-
ematical approaches, yet we regret that they may be perceived by nonanalytic chemists as impor-
tant obstacles in approaching molecular electrochemistry. For this reason, in this chapter, we take
advantage of the fact that most of these precise approaches are extremely well exposed in popular
electrochemical textbooks [1] to try to present most of the necessary electrochemical basis in

* They intervene as soon as heterogeneous reactants or phase boundaries are involved in the reaction medium, for example,
as in phase-transfer catalysis. In fact, the conscious (or even subconscious) use of spatial structuring of solutions is not
a privilege of electrochemists: nature uses the same phenomenon in most of its reactions, as in the proton transfer pump
crucial to ATP synthesis or in the photosynthetic chain.

© 2016 by Taylor & Francis Group, LLC

 6 Organic Electrochemistry

words and concepts using as much as possible references (or antireferences) to analogous concepts
of homogeneous chemistry. Thus, we hope that this chapter may constitute both a whole and a
guide to further and more specialized readings in electrochemistry. Yet there are three excep-
tions, each dealing with kinetic aspects, in which we had to break our resolution. The first two
concern electron transfer theories, and the third relates to electrochemical kinetics in the presence
of follow-up chemical reactions. Although these three points, and their pertinent derivations, are
in our opinion very important for a fine understanding of electrochemical processes and capabili-
ties, we suggest that the reader not interested in the mathematical body may skip the equations but
nevertheless follow the corresponding text.
This chapter is divided into three parts. In the first, basic definitions and their consequences for
homogeneous chemistry are presented. The second deals with the fundamental aspects of elec-
trode phenomena, whereas the third discusses the problem of mass transfer at electrodes and its
consequences for electrochemical kinetics. The particular problems and concepts associated with
preparative-scale electrolysis are presented in a separate chapter (Chapter 10).

II. Fundamental Aspects of Electron Transfer Reactions

A.  xidation–Reduction Reactions versus Electron Transfer
O
Reactions in Organic Chemistry and Electrochemistry
1. Oxidation–Reduction versus Electron Transfer Reactions
In homogeneous chemistry, pure electron transfer reactions are seldom encountered. Indeed, with
the exception of a few examples, electron transfers are often associated with atom or group trans-
fers. This usually results in a confused notion of the nature of oxidation–reduction reactions. For
example, the reaction of a ketone with sodium in alcohol to afford the corresponding alcohol, via
the sequence in the following [2] (see also Chapters 13 and 14),

Na – ROH Na ROH
C O C O C OH CH O– CH OH (1.1)

is termed a reduction. The same term is used for the Meerwein–Ponndorf–Verley reaction, which is
supposed to involve a concerted cyclic transition state [3,4]:

AI AI
O O O O OH
CH3 CH3
(1.2)
C C C C C
H CH3 H CH3 H

Similarly, reactions of metallic hydrides of aluminum or boron, in which the hydride is transferred
to the carbon (Equation 1.3 [5], or 1.4 [6,7]), are also considered reductions [7]):

Solv Solv
H H H
–Solv
C + C AIH–2 C AIH–2 C
+ Li , AIH–4

O Solv Solv O H O H OH (1.3)

Li+ Li+

Solv Solv Solv Solv

Solv Solv

© 2016 by Taylor & Francis Group, LLC

 Basic Concepts 7

O O
C H C H

ROH
C O + BH4– H O H O (1.4)
– –
B R B R
H H H H
H H

Although the preceding four reactions all obey the same stoichiometry for the carbonyl–alcohol
transformation and thus involve the same variation in the oxidation state of the carbon atom, they
are obviously different. Sodium reduction, in Equation 1.1, supposedly involves single electron [8]
and proton transfers in a succession of separate steps; conversely, in reactions (1.2) through (1.4),
groups or atoms are transferred.
The same confused notions also exist for oxidation reactions, the problem being even more sub-
tle. For example, permanganate is presented in most introductory textbooks as a typical oxidant
corresponding to the half-reaction in Equation 1.5:

MnO 4 − + 5e + 8H +  Mn 2+ + 4H 2O (1.5)

This, associated with the classic one-electron oxidation of ferrous to ferric salts by permanganate,
for example, may lead to the implicit notion that permanganate actually sequentially accepts elec-
trons in a similar way as the carbonyl group in Equation 1.1. The fact that this is not always the case
in practice is clearly evidenced by the mechanism of alcohol or aldehyde oxidation by permanganate
to ketones or carboxylic acids. Indeed, it is generally accepted that the mechanism of acidic oxida-
tion of aldehydes by permanganate involves no electron transfer steps but rather atom transfers as
in the sequence of Equations 1.6 through 1.8 (where B− is one of the bases present in the reaction
medium) to afford the carboxylic acid and an unstable manganese (V) moiety, which rapidly evolves
into MnO2 or Mn2+ according to the pH of the solution [9].

R R
C O + H3O+ C O+ – H + H2O (1.6)
H H

H H
–
R C O R C O
(1.7)
O+ MnO3 O MnO3

H H

H
C O
B– R
BH + R – CO2H + MnO–3 (1.8)
HO MnO3

Similarly, a reaction proceeding through a sequence of one-electron transfers and chemical steps,
such as pinacol formation from a ketone (Equations 1.9 and 1.10),

R R R
Na/Ng +BH
C O C O– C OH (1.9)
+B–
R΄ R΄ R΄

© 2016 by Taylor & Francis Group, LLC

 8 Organic Electrochemistry

R R
R R
R R R΄ R΄
BH
C OH + C O– C C R΄ C C R΄ (1.10)
R΄ R΄
O O– OH OH
H

can be reversed via a totally different sequence of steps involving atom transfers as in the classic
glycol oxidation to ketones by lead tetraacetate as follows [10]:

C OH C O Pb(OAc)3
+ Pb(OAc)4 + AcOH (1.11)
C OH C OH

C OH Pb(OAc)3 C O
Slow
Pb(OAc)2 + AcOH (1.12)
C OH C O

C O C O
Pb(OAc)2 + Pb(OAc)2 (1.13)
C O C O

2. Outer Sphere and Inner Sphere Electron Transfers

The preceding examples, which were purposely restricted to well-known reactions of carbonyl
and related functions, illustrate the large ambiguities associated with oxidation–reduction notions
in organic chemistry. As suggested earlier, these ambiguities certainly stem from the fact that
more attention is given to the overall transformation of one of the reactants (the substrate of
interest) than to the other(s) (the reagents). Indeed, in the ketone-to-alcohol reductions described,
more interest is devoted to the ketone than to the coreactant [Na, Al(OR)3, Li + AlH4−, or BH4−].
When the complete stoichiometrics are considered, it appears more clearly that all four reactions
(Equations 1.1 through 1.4) are totally different though substrate and product of interest are for-
mally the same.
On the other hand, when one thinks in terms of electrochemical reductions or oxidations, special
attention is devoted to the coreactant, that is, to the electrode that provides or accepts electrons.
Thus, in order to discuss or compare electrochemical reactions with their organic analogs, it is
of the utmost importance to use more precise terms than the so inaccurate reduction or oxidation
notions. A similar problem has been addressed in the inorganic and organometallic fields. Indeed, it
was early recognized that oxidation–reduction reactions at metal centers must be classified accord-
ing to two types: outer sphere and inner sphere reactions.* A typical example of the inner/outer
sphere dichotomy is given in Equations 1.14 and 1.15, which relate to chromium(II) oxidations by
cobalt(III) complexes.

* Another complementary concept, named concerted electron transfer, which bridges the gap between homogeneous and
electrochemical electron transfers was introduced by Savéant [2d] (see also Chapter 13).

© 2016 by Taylor & Francis Group, LLC

 Basic Concepts 9

Outer sphere (electron transfer) reaction [11]:

Cr 2+ + Co( III ) (NH 3 )63+ → Cr 3+ + Co( II ) (NH 3 )6 2+ (1.14)

Inner sphere (ligand transfer) reaction [11,12]:

Cr 2+ + Co( III ) (NH 3 )5 Cl 2+ → Cr ( III )Cl 2+ + Co( II ) (NH 3 )52+ (1.15)

Besides their relatively close stoichiometrics, the fact that the fundamental nature of the reactions
differs is evidenced by the acceleration by a factor of approximately 6 × 109 in the rate constant
when a chlorine ligand is involved in the transition state of the process.
Outer sphere electron transfers correspond to situations in which an electron is transferred with-
out the necessity of bond formation or bond cleavage between or within the reactants. The electron
is then transferred when the partners are sufficiently close to allow orbitals of suitable geometries
to overlap. The energetic stabilization required is of the order of 1 kcal/mol, which is considerably
smaller than that corresponding to any bond formation. The ketone reduction by sodium metal in
Equation 1.1 is considered to belong to this class of electron transfer. Similarly, owing to the usual
poor ability of electrodes in establishing bonds with the electroactive molecules, most of the elec-
trochemical electron transfers pertain to this group.* Interestingly, theories have been developed for
outer sphere electron transfers that allow reasonable predictions of their rate constants and activa-
tion energies (see Sections II.C and III.C).
Note that this definition does not imply that the products obtained upon electron transfer must be
stable, but only that the electron transfer activation process does not imply any important molecular
rearrangement. Indeed, one or both of the products may chemically evolve through fast follow-up
reactions as in the reaction sequences (1.1) or (1.9) and (1.10). Under some specific circumstances,
the electron transfer step may be strongly coupled with the chemical reaction expected to follow
would a pure outer sphere mechanism be taking place. This is termed concerted (outer sphere)
electron transfer [2d].
Inner sphere reduction or oxidation is normally restricted to bond formation between the reac-
tants in the transition state. For example, the chromium (II) oxidation in Equation 1.15 has been
shown to involve a chloride bridge between the chromium and cobalt centers as depicted in the fol-
lowing activated complex structure [12]:
#
Cr 2+  Cl  Co( III ) (NH3 )5  (1.16)
 

The organic chemical reduction–oxidations presented in the reaction sequences (1.2), (1.3), (1.4),
(1.7), or (1.11) through (1.13) belong to this class. Obviously, because an electrode is considered
able only to supply or accept electrons, this class of reduction–oxidation reactions should not be
observed in electrochemistry. However, this is not a clear-cut problem. Indeed, crucial interactions
with the electrode surface (e.g., organometallic partial bonding, chemisorption, physisorption) may
be crucially involved in the overall electron transfer process although the electrochemical kinetic
signature remains characteristic of a classical outer sphere case [13].
In our opinion, a third class of reduction–oxidation reactions exists, which is not clearly encom-
passed by one of the two just mentioned. It corresponds to the cases in which there really is an
electron transfer (i.e., not a group or atom transfer), but the latter is concerted with bond breaking or
formation within one of the reactants. It was proposed that the phrase concerted electron transfer

* This is not completely true, and a weak chemical interaction with the substrate undergoing the electron transfer step may
be crucial. This is always the case in electrocatalysis (e.g., proton reduction, fuel cells) but is hard to observe for organic
or organometallic cases. However, there are several perfectly documented examples in the recent literature [13b and
references therein].

© 2016 by Taylor & Francis Group, LLC

 10 Organic Electrochemistry

be used to refer to such situations [2d, 14–16]. A characteristic example of this class is given by the
reduction of alkyl halides, represented as follows:

RR′R′′C − X + e → RR′R′′C• + X − (1.17)

Indeed, it is now considered that carbon–halide bond cleavage is concerted with electron uptake
(see References 2d,14,15
−
as well as Chapter 24), that is, there is no intermediacy of an anion radical,
such as [ RR′R′′C − X],• during the electron transfer [15]. These cases must be contrasted with those,
such as the following aryl halide reduction:

Cl + e – Cl + Cl–, etc (1.18)

in which the electron is taken up (or lost) without drastic molecular rearrangement [14,16], to afford
an anion radical (or a cation radical in oxidations), although the latter may be extremely short-lived.
Formally, the carbonyl reduction in Equation 1.l should fall in this class of reaction, since it is usu-
ally considered that the π-carbonyl bond is broken (1.2) upon electron transfer to yield a ketyl anion
radical (Equation 1.20) that is better described as a tautomer of the delocalized one in Equation 1.19
than by a simple mesomeric form due to the ion pairing by the alkaline cation:

C O–

C O+e (1.19 and 1.20)

C O–

Yet the nature of the bond cleaved, especially when the latter is involved in extended delocalizations
as in aromatic ketones, and the fact that the skeleton of the molecule remains intact, may explain
why these reductions are generally considered as belonging to the outer sphere class.
From Table 1.1, which summarizes this discussion, it is seen that outer sphere and inner sphere
electron transfers have their exact analogs in both fields of organic chemistry and electrochemistry.

Table 1.1
Chemical and Electrochemical Reductions or Oxidations in Organic Chemistry
Bond Breaking or Follow-Up Examples
Formation in the Chemical
Designation Transition State Reaction Chemical Electrochemical
Outer sphere No No Na
Anthracene → Anthracene •
Anthracene + e  Anthracene •
electron transfer
No Yes ArCH3 + Fe(III) ⇌ ArCH3 •  + + Fe(II) ArCH3−e ⇌ ArCH3•  +
ArCH3 •  + + base → ArCH2•,… ArCH3 •  + + base → ArCH2•,…
Concerted No No ? RX + e→R• + X−
(outer sphere)
electron transfer
Ag
Inner sphere Within reactants Yes Wurtz reaction PhCH 2 Cl + e  →…
electron transfer (see Reference 13b)
Group or atom Between reactants Frequent Meerwein–Ponndorf reaction Invoked to interpret the effect of
transfer additives or electrode surface
states (as in the Kolbe reaction)

© 2016 by Taylor & Francis Group, LLC

 Basic Concepts 11

The third class, that is, concerted (outer sphere) electron transfer, is not easily recognized in organic
chemistry, at least to the best of our knowledge. The fourth class, that is, inner sphere group trans-
fers, deals with the peculiar properties of special reactants in organic chemistry or with those of
special electrode materials in electrochemistry.
At this point, it should be emphasized that there is a large body of outer sphere or inner
sphere electron transfer reactions identified and used in electrochemistry, whereas this class
of reactions is less developed in organic chemistry. Conversely, there is an extensive variety
of chemicals designed for specific group or atom transfer in reduction–oxidation reactions in
organic chemistry, but this is an area that is not very developed in molecular electrochemistry.
This certainly originates from the obvious fact that the reductive or oxidative strength of an
electrode can be varied over a wide range and adjusted with considerable precision because
of the easy control of the electrode potential. This advantage is not matched in homogeneous
organic chemistry owing to the discrete number of electron transfer reagents, particularly for
reductions. On the contrary, surface modifications and reactivities, especially under the condi-
tions of the large electrical fields encountered in electrochemistry (see Section III.4), are not
easy to design and control within the present state of the art, whereas owing to the extensive
development of organic [7], inorganic, and organometallic [17] chemistry, a large variety of
specific agents is made available. However, the apparent disadvantage of electrochemistry in the
latter area exists only when the electrode is considered as the only reactant affecting the sought
reaction. Indeed, specific chemicals (catalytic or stoichiometric reactants) that affect a desired
transformation on a substrate of interest may easily be electrochemically generated or recycled
as discussed in this book [18].

B. Standard Potentials: What They Mean and What They Do Not Mean
1. Standard Potentials
When considering a reaction between a possible electron donor and a possible electron acceptor, it is
important to decide a priori whether it will take place or not. This is usually answered by compari-
son of the standard (reduction) potentials E0 pertinent to each reactant. Indeed, when one considers
the possible reaction in the following,
− +
A + D  A• + D • (1.21)

the corresponding equilibrium constant K is related to the difference between the standard
0 0 •  −
(reduction) potentials E A/A − and E D+ /D of the A/A and D•  + /D couples, respectively. It follows
from the expression of K (F is the Faraday, R is the perfect gas constant and T the absolute
temperature)
0
F ( EA / A−
− E0 + )/ RT
K =e
D /D

0 0
that at equilibrium, Equation 1.21 should be displaced toward the right-hand side when EA/A −  ED +/D

and to the left-hand side when the converse is true (however, see Section II.B.6). When the dif-
ference between the values of the two standard reduction potentials is small, the reactant(s) and
product(s) equilibrium concentrations obviously depend not only on the potential difference but also
greatly on the initial composition of the solution. −
According to its definition, the standard (reduction)
−•
potential of the A/A • couple is the standard
electromotive force of a cell in which an A/A electrode is opposed to a normal hydrogen electrode
(NHE) whose potential is assigned to zero by convention.
−
A+ e  A• (E 0 ) (1.22)

© 2016 by Taylor & Francis Group, LLC

Other documents randomly have
different content
Welcome to our website – the ideal destination for book lovers and
knowledge seekers. With a mission to inspire endlessly, we offer a
vast collection of books, ranging from classic literary works to
specialized publications, self-development books, and children's
literature. Each book is a new journey of discovery, expanding
knowledge and enriching the soul of the reade

Our website is not just a platform for buying books, but a bridge
connecting readers to the timeless values of culture and wisdom. With
an elegant, user-friendly interface and an intelligent search system,
we are committed to providing a quick and convenient shopping
experience. Additionally, our special promotions and home delivery
services ensure that you save time and fully enjoy the joy of reading.

Let us accompany you on the journey of exploring knowledge and

personal growth!

ebooknice.com