Structure Energetics and Reactivity in Chemistry Series (SEARCH Series)

Series Editors

JOEL F. LIEBMAN Department of Chemistry and Biochemistry University of Maryland Baltimore County Baltimore, MD 21228

ARTHUR GREENBERG Department of Chemistry University of North Carolina at Charlotte Charlotte, NC 28223

The volumes in this series are comprised of state-of-the-art reviews, ex­plicitly pedagogical in nature, in which specific topics are treated in depth. The series acronym SEARCH reflects the interplay between Struc­ture, Energy And Reactivity in CHemistry and how these are also man­ifested in physical properties and biological activities.

Other titles in the Series

Volume I Mesomolecules: From Molecules to Materials Edited by G. David Mendenhall, Arthur Greenberg, and Joel F. Uebman

Volume ill Active Oxygen in Biochemistry Edited by Joan Selverstone Valentine, Christopher S. Foote, Arthur Greenberg, and Joel F. Uebman

Editorial Advisory Board

WESTON T. BORDEN Department of Chemistry University of Washington Seattle, WA 98195

JULIAN A. DAVIES Department of Chemistry University of Toledo Toledo, OH 43606

GAUTAM R. DESIRAJU School of Chemistry University of Hyderabad Hyderabad, India 500134

FRANCOIS N. DIEDERICH Eidgenossische Technische

Hochschule (ETH) Laboratorium fur Organische

Chemie CH-8092 ZUrich, Switzerland

DENNIS A. DOUGHERTY Dep~rtment of Chemistry California Institute of Technology Pasadena, CA 91125

RICHARD D. GANDOUR Department of Chemistry Virginia Polytechnic Institute and

State University Blacksburg, VA 24601

SHARON G. LIAS Chemical Thermodynamics

and Kinetics Division National Institute of Standards

and Technology Gaithersburg, MD 20899

ALAN P. MARCHAND Department of Chemistry University of North Texas Denton, TX 76203

JOSE ARTUR MARTINHO SIMOES Departmento de Quimica e Bioquimica Faculdade de Ciencias Universidade de Lisboa 1700 Lisboa, Portugal

JOAN MASON Department of Chemistry Open University Milton Keynes MK7 6AA UK

ROBERT A. MOSS Department of Chemistry Rutgers University Piscataway, NJ 08855

BRUCE E. SMART E.!. Du Pont de Nemours & Co., Inc. Central Research and Development Experimental Station Wilmington, DE 19880

JOAN SEL VERSTONE VALENTINE Department of Chemistry and

Biochemistry University of California,

Los Angeles Los Angeles, CA 90095

DEBORAH V AN VECHTEN Space Sciences Division Naval Research Laboratory Washington, DC 20375

ACTIVE OXYGEN

IN CHEMISTRY

EDITORS: CHRISTOPHER S. FOOTE

University of California at Los Angeles

"OAN SELVERSTONE VALENTINE University of California at Los Angeles

ARTHUR GREENBERG University of North Carolina at Charlotte

"OEL F. LIEBMAN University of Maryland Baltimore County

BLACKIE ACADEMIC &. PROFESSIONAL An Imprint of Chapman & Hall

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Published by Blackle Academic and Professional, an imprint of Cbapman & Hall, Wester Cleddens Road, Bisbopbriggs, Glasgow G64 2NZ

Chapman & Hall, 2-6 Boundary Row, LondonSE18HN, UK

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Chapman & Hall India, R. Seshadri, 32 Second Main Road, CIT East, Madras 600 035, India

First edition 1995

© 1995 Chapman & Hall

Softcover reprint of the hardcover I st edition 1995

Apart from any fair dealing for the purposes of research or private study, or criticism or review, as permitted under the UK Copyright Designs and Patents Act, 1988, this publication may not be reproduced, stored, or transmitted, in any form or by any means, without the prior pennission in writing of the publishers, or in the case of reprographic reproduction only in accordance with the temlS of the licences issued by the Copyright Licensing Agency in the UK, or in accordance with the temlS of licences issued by the appropriate Reproduction Rights Organization outside the UK. Enquiries concerning reproduction outside the terms stated here should be sent to the publishers at the Glasgow address printed on this page.

The publisher makes no representation, express or implied, with regard 10 the accuracy of the information contained in this book and cannot accept any legal responsibility or liability for any elTors or omissions that may be made.

A catalogue record for this book is available from the British Library

Library of Congress Cataloging-in-Publication Data available

Active oxygen in chemistry I editors, Christopher S. Foote ... (et a1.) . p. em. - (Structure energetics and reactivity in chemistry ;

v.2) Includes bibliographical references and index. ISBN 978-0-7514-0371-8 ISBN 978-94-007-0874-7 (eBook)

I. Active oxygen in chemistry. I. Foote, Christopher S. II. Series. QD181.01A28 1995 94-20876 546'.721 59-dc20 CIP

DOI 10.1007/978-94-007-0874-7

Contents

Preface vii

Series Preface ix

Contributors xi

1 Overview of Energetics and Reactivity of Oxygen 1 Raymond Y. N. Ho, Joel F. Liebman, and Joan Selverstone Valentine

2 Autoxidation 24 Cheves Walling

3 Superoxide and Hydroxyl Radical Chemistry in Aqueous Solution 66 Benon H. ]. Bielski and Diane E. Cabelli

4 Properties and Reactions of Singlet Dioxygen 105 Christopher S. Foote and Edward L. Clennan

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vi Contents

5 Reactions of Hydroperoxides and Peroxides 141 Pat Dussault

6 Catalytic Oxidations with Oxygen: An Industrial Perspective 204 Dennis Riley and Jerry Ebner

7 Reactions of Oxygen Species in the Atmosphere 249 Roger Atkinson

8 Reactive Oxygen Species in Natural Waters 280 Neil V. Blough and Richard G. Zepp

Index 335

Preface

The field of "Oxygen Activation" has attracted considerable interest recently, not only because it presents challenges in those fields of basic research that aim to understand the fundamental aspects of chemical and biological reactions that involve dioxygen, but also because of its wide range of practical implications in such diverse fields as materials science, atmospheric science, synthesis of pharmaceuticals and other organic compounds, and medicine. This is the first of two volumes focusing on the subject of oxygen activation, the first slanted towards chemistry and the second towards biological chemistry. We planned these volumes to be more general than many monographs of this sort, not as detailed sum­maries of the authors' own research, but as general overviews of the field. Our choice of topics was strongly influenced by the syllabus for a course entitled 1/ Oxygen Chemistry", which two of us have twice taught jointly at UCLA. Definition of important issues, horizons, and future prospects was an important goal, and, although totally comprehensive coverage was not possible, we believe that we have chosen a representa­tive selection of research topics current to the field. We have targeted this

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viii Preface

work to a diverse audience, from professionals in fields from physics to medicine to beginning graduate students, who are interested in rapidly acquiring the basics of this field. Intending that these volumes will find use as textbooks, we have edited the chapters to be fairly uniform, at a level accessible to chemically literate readers with a bachelor's degree in science or engineering. We hope that readers will find these volumes useful in providing both an introduction to and an overview of a field that we have found to be both challenging and rewarding.

CHRISTOPHER S. FOOTE

JOAN SELVERSTONE VALENTINE

ARTHUR GREENBERG

JOEL F. LIEBMAN

Series Preface

The purpose of this series is the presentation of the most significant re­search areas in organic chemistry from the perspective of the interplay and inseparability of structure, energetics, and reactivity. Each volume will be modeled as a text for a one-semester graduate course and will thus provide groundwork, coherence, and reasonable completeness. In this context, we have made the editorial decision to defer to the authors the choice of the desired blend of theory and experiment, rigor and intu­ition, practice and perception. However, we asked them to engage in the spirit of this venture and to explain to the reader the basis of their understanding and not just the highlights of their findings. For each vol­ume, and each chapter therein, we have aimed for both a review and a tutorial of a major research area. Each volume will have a single theme, unified by the common threads of structure, energy, and reactivity for the understanding of chemical phenomena.

Structure, energetics, and reactivity are three of the most fundamental, ubiquitous, and therefore seminal concepts in organic chemistry. The concept of structure arises as soon as even two atoms are said to be bonded, since it is there that the concept of bond length and interatomic separation begins. Three-atom molecules already introduce bond angle into our functioning vocabulary, while four atoms are needed for the introduction of the terms planarity, nonplanarity, and dihedral angles. Of course, most organic chemists are interested in molecules of more than four atoms, so new shapes (tetrahedra, cubes, dodecahedra, prisms, and numerous exotic polyhedra) and new degrees of complexity arise. These

ix

x Series Preface

new molecular shapes, in tum, function as templates for the next molec­ular generation. Still, the basic assumption remains: molecular structure determines energy and reactivity, and even though Van't Hoff, LeBel, and Sachse explained chemical reality with palpable molecular models over a century ago, we still do much the same thing on the screens of personal computers.

The concept of energetics arises in chemistry as soon as there is a proton and an electron and remains with us throughout our discipline. There are the fundamental, experimentally measurable quantities of bond energies, proton affinities, ionization potentials, pKa values, and heats of formation. There are the derived quantities such as strain and resonance energies, acidity, and basicity. There are also the widely used, generally understood, and rather amorphous concepts such as delocali­zation, conjugation, and aromaticity. Indeed, the shape, conformation, and therefore function of a protein are determined by a balance of energetics contributions-resonance in the peptide linkage, hydrogen bonding, hin­dered rotation of a disulfide, Van der Waals forces, steric repulsion, Cou­lombic interactions and salt bridges, and solvent interactions.

The concept of reactivity inseparably combines structure and energet­ics and introduces more concepts and words: stereospecificity, intramolec­ularity, nucleophilicity, catalysis, entropy of activation, steric hindrance, po­larizability, hard and soft acids and bases, Hammett/Taft parameters. Reactivity is a more difficult concept than structure and energetics. One must spec­ify reaction conditions and usually accompanying reagents, since reac­tivity generally refers to two species or at least two seemingly disjoint parts of the same molecule.

Structure, energetics, and reactivity in chemistry have been probed by a plethora of experimental and theoretical methods. These tools have different degrees of accuracy and applicability, and consensus is rare as to when our understanding is deemed adequate. Indeed, diverse ap­proaches-heats of hydrogenation and Hartree-Fock calculations, line in­tensities and LDso values, ease of substitution and of sublimination, cou­pling constants and color-all contribute to the special blend of rigor and intuition that characterizes modem organic chemistry.

As people, and not just as scientists and editors, we wish to acknowl­edge the unity of the intellect and the emotions. We are grateful for the love and support of our families and for the inspiration, agitation, and stimulation from our mentors, colleagues, and students, and so we dedicate these volumes "To Research and to Reason, To Family and to Friendship."

JOEL F. LIEBMAN

Baltimore, Maryland AR1HUR GREENBERG

Charlotte, North Carolina

Contributors

Professor Roger Atkinson Statewide Air Pollution Research Center Department of Soil and Environmental Sciences University of California, Riverside Riverside, CA 92521

Dr. Benon H. J. Bielski Department of Chemistry Brookhaven National Laboratory Upton, NY 11973

Professor Neil V. Blough Department of Chemistry University of Maryland College Park, MD 20742

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xii Contributors

Dr. Diane E. Cabelli Department of Chemistry Brookhaven National Laboratory Upton, NY 11973

Professor Edward L. Clennan Department of Chemistry University of Wyoming Laramie, WY 82071

Professor Pat Dussault Department of Chemistry University of Nebraska, Lincoln Lincoln, NE 68588 e-mail: dussault@unlinfo.unl.edu

Dr. Jerry Ebner Monsanto Company 800 North Lindbergh Blvd. St. Louis, MO 63167

Professor Christopher S. Foote Department of Chemistry and Biochemistry University of California, Los Angeles Los Angeles, CA 90095 e-mail: csf@argon.chem.ucla.edu

Raymond Y. N. Ho Department of Chemistry and Biochemistry University of California, Los Angeles Los Angeles, CA 90095 e-mail: ho@uclac1.chem.ucla.edu

Professor Joel F. Liebman Department of Chemistry and Biochemistry University of Maryland Baltimore County Baltimore, MD 21228 e-mail: jliebman@umbc2.umbc.edu

Dr. Dennis Riley Monsanto Company 800 North Lindbergh Blvd. St. Louis, MO 63167

Professor Joan Selverstone Valentine Department of Chemistry and Biochemistry University of California, Los Angeles Los Angeles, CA 90095 e-mail: jsV@Chem.uc1a.edu

Professor Emeritus Cheves Walling Box 537 Jaffrey, NH 03452

Dr. Richard G. Zepp U.S. Environmental Protection Agency Environmental Research Lab College Station Road Athens, GA 30613 e-mail: rzepp@athens.ath.epa.gov

Contributors xiii