Elements of Molecular and Biomolecular Electrochemistry : An Electrochemical Approach to Electron Transfer Chemistry

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ISBN: 9780471445739 | 0471445738
Cover: Hardcover
Copyright: 4/28/2006

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This book is based on the George Fisher Baker Lecture given by Jean-Michel Savéant at Cornell University in Fall 2002. * The first book focusing on molecular electrochemistry * Relates to other fields, including photochemistry and biochemistry * Outlines clearly the connection between concepts, experimental illustrations, proofs and supporting methods * Appendixes to provide rigorous demonstrations to prevent an overload of algebra in the main text * Applications-oriented, focused on analyzing the results obtained rather than the methodology

Preface

xiii

CHAPTER 1 Single Electron Transfer at an Electrode

(77)

1.1 Introduction

(1)

1.2 Cyclic Voltammetry of Fast Electron Transfers. Nernstian Waves

(8)

1.2.1 One-Electron Transfer to Molecules Attached to the Electrode Surface

(3)

1.2.2 One-Electron Transfer to Free-Moving Molecules

(5)

1.3 Technical Aspects

(18)

1.3.1 The Cyclic Voltammetry Experiment. Faradaic and Double-Layer Charging Currents. Ohmic Drop

(10)

1.3.2 Other Techniques. Convolution

(8)

1.4 Electron Transfer Kinetics

(34)

1.4.1 Introduction

(2)

1.4.2 Butler–Volmer Law and Marcus–Hush Model

(14)

1.4.3 Extraction of Electron Transfer Kinetics from Cyclic Voltammetric Signals. Comparison with Other Techniques

(13)

1.4.4 Experimental Testing of the Electron Transfer Models

(5)

1.5 Successive One-Electron Transfers vs. Two-Electron Transfers

(7)

1.5.1 Introduction

(2)

1.5.2 Cyclic Voltammetric Responses. Convolution

(5)

1.5.3 Response of Molecules Containing Identical and Independent Reducible or Oxidizable Groups

(6)

1.5.4 An Example of the Predominating Role of Solvation: The Oxidoreduction of Carotenoids

(3)

1.5.5 An Example of the Predominating Role of Structural Changes: The Reduction of trans-2,3-Dinitro-2-butene

(2)

References and Notes

(3)

CHAPTER 2 Coupling of Electrode Electron Transfers with Homogeneous Chemical Reactions

(104)

2.1 Introduction

(2)

2.2 Establishing the Mechanism and Measuring the Rate Constants for Homogeneous Reactions by Means of Cyclic Voltammetry and Potential Step Chronoamperometry

(45)

2.2.1 The EC Mechanism

(12)

2.2.2 The CE Mechanism

(2)

2.2.3 The Square Scheme Mechanism

(2)

2.2.4 The ECE and DISP Mechanisms

(6)

2.2.5 Electrodimerization

102

(4)

2.2.6 Homogeneous Catalytic Reaction Schemes

106

(13)

2.2.7 Electrodes as Catalysts

119

(2)

2.2.8 Numerical Computations. Simulations. Diagnostic Criteria. Working Curves

121

(4)

2.3 Application of Redox Catalysis to the Kinetic Characterization of Fast Follow-up Reactions

125

(7)

2.3.1 Principle and Achievements of the Method

125

(3)

2.3.2 Comparison with Fast Cyclic Voltammetry and Laser Flash Photolysis

128

(1)

2.3.3 Determination of the Standard Potential for the Formation of Very Unstable Primary Intermediates

129

(2)

2.3.4 Redox Catalysis of Electrocatalytic Processes

131

(1)

2.4 Product Distribution in Preparative Electrolysis

132

(8)

2.4.1 Introduction

132

(1)

2.4.2 General Features

133

(3)

2.4.3 Product Distribution Resulting from Competition Between Follow-up Reactions

136

(2)

2.4.4 The ECE–DISP Competition

138

(1)

2.4.5 Other Reactions Schemes

139

(1)

2.5 Chemical Classification and Examples of Coupled Reactions

140

(27)

2.5.1 Coupling of Single Electron Transfer with Acid–Base Reactions

140

(8)

2.5.2 Electrodimerization

148

(3)

2.5.3 Electropolymerization

151

(1)

2.5.4 Reduction of Carbon Dioxide

152

(2)

2.5.5 H-Atom Transfer vs. Electron + Proton Transfer

154

(4)

2.5.6 The SRN1 Substitution. Electrodes and Electrons as Catalysts

158

(5)

2.5.7 Conformational Changes, Isomerization, and Electron Transfer

163

(4)

2.6 Redox Properties of Transient Radicals

167

(11)

2.6.1 Direct Electrochemical Approach

167

(5)

2.6.2 Application of Laser Flash Electron Injection

172

(3)

2.6.3 Photomodulaltion Voltammetry

175

(2)

2.6.4 Application of Redox Catalysis

177

(1)

2.7 Electrochemistry as a Trigger for Radical Chemistry or Ionic Chemistry

178

(1)

References and Notes

179

(3)

CHAPTER 3 Electron Transfer, Bond Breaking, and Bond Formation

182

(69)

3.1 Introduction

182

(2)

3.2 Dissociative Electron Transfer

184

(10)

3.2.1 Thermodynamics. Microscopic Reversibility

184

(3)

3.2.2 The Morse Curve Model

187

(5)

3.2.3 Values of the Symmetry Factor and Variation with the Driving Force

192

(1)

3.2.4 Entropy of Activation

193

(1)

3.3 Interactions Between Fragments in the Product Cluster

194

(9)

3.3.1 Influence on the Dynamics of Dissociative Electron Transfers

195

(2)

3.3.2 Typical Example: Dissociative Electron Transfer to Carbon Tetrachloride

197

(2)

3.3.3 Stabilities of Ion-Radical Adducts as a Function of the Solvent

199

(1)

3.3.4 Dependency of In-Cage Ion–Radical Interactions on the Leaving Group

200

(3)

3.4 Stepwise vs. Concerted Mechanisms

203

(15)

3.4.1 Introduction

203

(1)

3.4.2 Diagnostic Criteria

204

(2)

3.4.3 How Molecular Structure Controls the Mechanism

206

(3)

3.4.4 Passage from One Mechanism to the Other upon Changing the Driving Force

209

(4)

3.4.5 Photoinduced vs. Thermal Processes

213

(3)

3.4.6 Does a Concerted Mechanism Mean That the Intermediate "Does Not Exist"?

216

(1)

3.4.7 π and σ Ion Radicals. Competition Between Reaction Pathways

216

(2)

3.5 Cleavage of Ion Radicals. Reaction of Radicals with Nucleophiles

218

(11)

3.5.1 Introduction

218

(1)

3.5.2 Heterolytic Cleavages. Coupling of Radicals with Nucleophiles

218

(7)

3.5.3 Homolytic Cleavages

225

(4)

3.6 Role of Solvent in Ion-Radical Cleavage and in Stepwise vs. Concerted Competitions

229

(10)

3.6.1 Introduction

229

(1)

3.6.2 Experimental Clues

230

(5)

3.6.3 A Simplified Model System

235

(4)

3.7 Dichotomy and Connections between SN2 Reactions and Dissociative Electron Transfers

239

(9)

3.7.1 Introduction

239

(1)

3.7.2 Experimental Approaches

240

(4)

3.7.3 Theoretical Aspects

244

(4)

References and Notes

248

(3)

CHAPTER 4 Molecular Catalysis of Electrochemical Reactions

251

(47)

4.1 Introduction

251

(1)

4.2 Homogeneous Molecular Catalysis

252

(16)

4.2.1 Contrasting Redox and Chemical Catalysis

252

(2)

4.2.2 The Reduction of Vicinal Dibromides. Outer- and Inner-Sphere Catalysts. Rates and Stereoselectivity

254

(6)

4.2.3 Homogeneous Chemical Catalysis of the Reduction of Carbon Dioxide. Synergistic Effect of Brönsted and Lewis Acids

260

(4)

4.2.4 Two-Step Chemical Catalysis of the Reduction of Alkyl Halides by Low-Valent Cobalamins and Cobinamides

264

(4)

4.3 Supported Molecular Catalysis (Immobilized Catalysts)

268

(28)

4.3.1 Redox and Chemical Catalysis at Monolayer and Multilayer Coated Electrodes

268

(2)

4.3.2 Catalysis at Monolayer Coated Electrodes

270

(9)

4.3.3 Permeation Through Electrode Coatings. Inhibition

279

(5)

4.3.4 Electron Hopping in Assemblies of Redox Centers

284

(3)

4.3.5 Catalysis at Multilayer Coated Electrodes

287

(5)

4.3.6 Combining an Electron-Shuttling Mediator with a Chemical Catalyst in a Multilayer Electrode Coating

292

(4)

References and Notes

296

(2)

CHAPTER 5 Enzymatic Catalysis of Electrochemical Reactions

298

(50)

5.1 Introduction

298

(1)

5.2 Homogeneous Enzymatic Catalysis

299

(16)

5.2.1 Introduction

299

(1)

5.2.2 The Ping-Pong Mechanism. Kinetic Control by Substrate and/or Cosubstrate

300

(6)

5.2.3 A Model Example: Glucose Oxidase with Excess Glucose

306

(1)

5.2.4 Molecular Recognition of an Enzyme by Artificial One-Electron Cosubstrates

307

(4)

5.2.5 Deciphering a Complex Electroenzymatic Response: Horseradish Peroxidase

311

(4)

5.3 Immobilized Enzymes in Monomolecular Layers

315

(25)

5.3.1 Introduction

315

(1)

5.3.2 The Ping-Pong Mechanism with an Immobilized Enzyme and the Cosubstrate in Solution

315

(8)

5.3.3 Antigen–Antibody Immobilization of Glucose Oxidase. Kinetic Analysis

323

(2)

5.3.4 Application to the Kinetic Characterization of Biomolecular Recognition

325

(7)

5.3.5 Immobilized Horseradish Peroxidase

332

(4)

5.3.6 Immobilization of Both the Enzyme and the Cosubstrate. Electron Transfer and Electron Transport in Integrated Systems

336

(4)

5.4 Spatially Ordered Multimonomolecular Layered Enzyme Coatings

340

(6)

5.4.1 Step-by-Step Antigen–Antibody Construction of Multimonomolecular Layer Enzyme Coatings

340

(2)

5.4.2 Reaction Dynamics with the Cosubstrate in Solution. Evidence for Spatial Order

342

(4)

References and Notes

346

(2)

CHAPTER 6 Appendixes

348

(122)

6.1 Single Electron Transfer at an Electrode

348

(25)

6.1.1 Laplace Transformation. Useful Definitions and Relationships

348

(1)

6.1.2 Cyclic Voltammetry of One-Electron Nernstian Systems. Current– and Charge–Potential Curves

348

(5)

6.1.3 Double-Layer Charging in Cyclic Voltammetry. Oscillating and Nonoscillating Behavior

353

(4)

6.1.4 Effect of Ohmic Drop and Double-Layer Charging on Nernstian Cyclic Voltammograms

357

(4)

6.1.5 Potential Step and Double Potential Step Chronoamperometry of Nernstian Systems

361

(1)

6.1.6 Overlapping of Double-Layer Charging and Faradaic Currents in Potential Step and Double Potential Step Chronoamperometry. Oscillating and Nonoscillating Behavior

361

(2)

6.1.7 Solvent Reorganization in Marcus–Hush Model

363

(5)

6.1.8 Effect of the Multiplicity of Electronic States in the Electrode

368

(3)

6.1.9 Cyclic Voltammetry of Two-Electron Nernstian Systems. Disproportionation

371

(2)

6.2 Coupling of Homogeneous Chemical Reactions with Electron Transfer

373

(65)

6.2.1 The EC Mechanism

373

(6)

6.2.2 The CE Mechanism

379

(3)

6.2.3 Double Potential Step Responses for Processes Involving First- or Second-Order Follow-up Reactions

382

(1)

6.2.4 The ECE and DISP Mechanisms

383

(8)

6.2.5 Electrodimerization

391

(7)

6.2.6 Competition Between Dimerization of and Electron Transfer to Intermediates

398

(5)

6.2.7 Homogeneous Catalysis

403

(11)

6.2.8 Product Distribution in Preparative Electrolysis

414

(24)

6.3 Electron Transfer, Bond Breaking, and Bond Formation

438

(3)

6.3.1 Contribution of the Cleaving Bond Stretching to Internal Reorganization of the First Step of the Stepwise Mechanism

438

(1)

6.3.2 Morse Curve Model of Intramolecular Dissociative Electron Transfer

439

(2)

6.4 Analysis of Supported Molecular Catalysis by Rotating Disk Electrode Voltammetry and Cyclic Voltammetry

441

(11)

6.4.1 Catalysis at Monolayer Electrode Coatings

441

(3)

6.4.2 Inhibition of Electron Transfer at Partially Blocked Electrodes

444

(1)

6.4.3 Equivalent Diffusion and Migration Laws for Electron Hopping Between Fixed Sites

445

(1)

6.4.4 Catalysis at Multilayered Electrode Coatings

446

(6)

6.5 Enzymatic Catalysis Responses

452

(17)

6.5.1 The Ping-Pong Mechanism in Homogeneous Enzymatic Catalysis

452

(5)

6.5.2 Catalysis and Inhibition in Homogeneous Systems

457

(5)

6.5.3 Catalysis at Multilayered Electrode Coatings

462

(7)

References and Notes

469

(1)

Glossary of Symbols

470

(11)

Index

481

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Elements of Molecular and Biomolecular Electrochemistry : An Electrochemical Approach to Electron Transfer Chemistry

Summary

Author Biography

Table of Contents

Supplemental Materials

FREE SHIPPING

Rent More, Save More! Use code: BBRENTAL

5% off 1 book, 7% off 2 books, 10% off 3+ books

Elements of Molecular and Biomolecular Electrochemistry : An Electrochemical Approach to Electron Transfer Chemistry

Summary

Author Biography

Table of Contents

Supplemental Materials

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