Contributors FRAN ADAR EDGAR F. MEYER, JR. J. 0. ALBEN YASH P. MYER H. BUDZIKIEWICZ AJAY PANDE G. W. CANTERS W. ROBERT SCHEIDT DAVID L. CULLEN JOHN CLARK SUTHERLAND R. H. FELTON J. H. VAN DER WAALS MARTIN GOUTERMAN CHARLES WEISS BARTON HOLMQUIST NAI-TENG YU THE PORPHYRINS Volume III Physical Chemistry, Part A Edited by DAVID DOLPHIN Department of Chemistry University of British Columbia Vancouver, British Columbia, Canada ACADEMIC PRESS New YORK SAN FRANCISCO LONDON 1978 A Subsidiary of Harcourt Brace Jovanovich, Publishers COPYRIGHT © 1978, BY ACADEMIC PRESS, INC. ALL RIGHTS RESERVED. NO PART OF THIS PUBLICATION MAY BE REPRODUCED OR TRANSMITTED IN ANY FORM OR BY ANY MEANS, ELECTRONIC OR MECHANICAL, INCLUDING PHOTOCOPY, RECORDING, OR ANY INFORMATION STORAGE AND RETRIEVAL SYSTEM, WITHOUT PERMISSION IN WRITING FROM THE PUBLISHER. ACADEMIC PRESS, INC. ILL FIFTH AVENUE, NEW YORK, NEW YORK 10003 United Kingdom Edition published by ACADEMIC PRESS, INC. (LONDON) LTD. 24/28 OVAL ROAD, LONDON NW1 7DX LIBRARY OF CONGRESS CATALOGING IN PUBLICATION DATA MAIN ENTRY UNDER TITLE: THE PORPHYRINS. INCLUDES BIBLIOGRAPHIES AND INDEXES. CONTENTS: V. 2 PT. B. STRUCTURE AND SYNTHESIS,—V. 3, PT. A. PHYSICAL CHEMISTRY, V. 5. PT. C. PHYSICAL CHEMISTRY. 1. PORPHYRIN AND PORPHYRIN COMPOUNDS. I. DOLPHIN, DAVID. [DNLM: 1. PORPHYRINS. WH190 P837] QD401.P825 54V.593 77-14197 ISBN 0-12-220103-5 ( V. 3 ) PRINTED IN THE UNITED STATES OF AMERICA 78 79 80 81 82 9 8 7 6 5 4 3 2 1 List of Contributors Numbers in parentheses indicate the pages on which the authors' contributions begin. FRAN ADAR* (167), Department of Biochemistry and Biophysics, University of Pennsylvania, Philadelphia, Pennsylvania 19174 J. O. ALBEN (323), Department of Physiological Chemistry, Ohio State University, College of Medicine, Columbus, Ohio 43210 H. BUDZIKIEWICZ (395), Institute of Organic Chemistry, Univer- sity of Cologne, Cologne, Germany G. W. CANTERS (531), Center for the Study of the Excited States of Molecules, Rijks Universiteit, Leiden, The Netherlands DAVID L. CULLEN (513), Department of Biochemistry and Biophysics, Texas A&M University, Texas Agricultural Ex- periment Station, College Station, Texas 77843 R. H. FELTON (347), School of Chemistry, Georgia Institute of Technology, Atlanta, Georgia 30332 MARTIN GOUTERMAN (1), Department of Chemistry, University of Washington, Seattle, Washington 98195 BARTON HOLMQUIST (249), Biophysics Research Laboratory, De- partment of Biological Chemistry, Harvard Medical School and the Division of Medical Biology, Peter Bent Brigham Hos- pital, Boston, Massachusetts 02115 * Present address: Instruments SA, Inc., Metuchen, New Jersey 08840. ix χ LIST OF CONTRIBUTORS EDGAR F. MEYER, JR. (513), Department of Biochemistry and Biophysics, Texas A&M University, Texas Agricultural Ex- periment Station, College Station, Texas 77843 YASH P. MYER (271), Department of Chemistry, State University of New York at Albany, Albany, New York 12222 AJAY PANDE (271), Department of Chemistry, State University of New York at Albany, Albany, New York 12222 W. ROBERT SCHEIDT (463), Department of Chemistry, University of Notre Dame, Notre Dame, Indiana 46556 JOHN CLARK SUTHERLAND* (225), Department of Physiology, California College of Medicine, The University of California, Irvine, California 92664 J. H. VAN DER WAALS (531), Center for the Study of the Excited States of Molecules, Rijks Universiteit, Leiden, The Nether- lands CHARLES WEISS (211), International Bank for Reconstruction and Development, Washington, D.C. 20433 NAI-TENG YU (347), School of Chemistry, Georgia Institute of Technology, Atlanta, Georgia 30322 * Present address: Biology Department, Brookhaven National Laboratory, Upton, New York 11973. General Preface Man cannot give a true reason for the grass under his feet why it should be green rather than red or any other color. Sir Walter Raleigh History of the World: Preface (1614) Just over two centuries after these words of Raleigh, Verdeil in 1844 converted chlorophyll to a red pigment which prompted him to suggest a structural relationship between chlorophyll and heme. Shortly thereafter, Hoppe-Seyler, in 1880, strengthened this hypothesis by showing the spec- tral resemblances between hematoporphyrin and an acid degradation product of chlorophyll. The final steps in these structural elucidations were initiated by Willstätter, and culminated in the heroic work of Hans Fischer who showed that but for two hydrogen atoms grass would indeed be red and that only two more hydrogen atoms would have ensured that Raleigh and his countrymen would indeed have been blue-blooded Englishmen. The close structural similarity between the porphyrins and chlorins gives little measure of the relationships among and the diversity of their numerous and important biochemical functions. All life on this planet relies directly on the central role of the chlorophylls and cytochromes in photosynthesis by means of which photonic energy is converted and stored as chemical energy. It is likely that long before oxygen was abun- dant in the Earth's atmosphere the cytochromes were responsible for respiration. With the advent of photosynthesis the oxygen produced is the xi xii GENERAL PREFACE terminal electron acceptor for all aerobic respiration. For many organisms the means by which oxygen is transported, stored, reduced, and activated are frequently mediated by heme proteins. In mammals, oxygen is trans- ported by the cooperative tetrameric protein hemoglobin and stored by monomeric myoglobin. When oxygen is reduced to water, in the terminal step of respiration, four electrons are transported via a series of cyto- chromes to cytochrome oxidase. Cytochrome oxidase contains two iron porphyrins and two copper atoms. In addition, nature also brings about one- and two-electron reductions to superoxide and peroxide. Both the decomposition and further activation of hydrogen peroxide are mediated by the heme proteins catalase and peroxidase. Furthermore, heme pro- teins function as both mono- and dioxygenases, and recently cytochrome P-450, which functions as a monooxygenase by combining properties of both oxygen binding and electron transport, has been shown to be impor- tant in a wide variety of biological hydroxylations. This brief insight into a few of the many central roles played by metal- loporphyrins in nature plus the challenges that porphyrins present to the inorganic, organic, physical, and biochemist suggest the wealth of knowl- edge that is documented in these areas. It is the objective of "The Porphyrins'' to present a full and critical coverage of all the major fields relating to porphyrins, their precursors, catabolic derivatives, and related systems in a manner that we trust will be useful to those in physics, chemistry, biochemistry, and medicine. The treatise consists of seven volumes. Volumes I and II (Structure and Synthesis, Parts A and B) cover nomenclature, history, geochemistry, synthesis, purification, and structural determination of porphyrins, metal- loporphyrins, and mono- and polypyrrolic compounds and related sys- tems. Volumes III, IV, and V (Physical Chemistry, Parts A, B, and C) cover electronic structure and spectroscopy including uv-vis, ORD, CD, MCD, mass, ir, resonance Raman, Mössbauer, Zeeman, NMR (diamagnetic, paramagnetic), ESR, and X-ray crystallography. In addi- tion, redox chemistry, electron transfer, aggregation, oxygenation, and solid state phenomena are included. Volumes VI and VII (Biochemistry, Parts A and B) cover the biosynthesis and enzymatic synthesis of porphy- rins, chlorophylls, and their precursors, and the chemistry and biochemis- try of the bile pigments and the roles of porphyrins and bile pigments in clinical chemistry. The structure and function of the major hemoproteins are also covered. It remains for me to thank my colleagues and co-workers for their support and assistance. A special debt of gratitude goes to my mentors: Alan Johnson who introduced me to these areas and who taught me why chlorophyll is green, and Bob Woodward who showed the world how to make chlorophyll and taught me why. DAVID DOLPHIN Preface Volume III (Physical Chemistry, Part A) contains chapters on various aspects of porphyrin spectroscopy including circular and magnetic circu- lar dichroism, electronic, infrared, resonance Raman, and Zeeman spec- troscopy. Chapters on porphyrin stereochemistry, X-ray crystallography, and mass spectroscopy of porphyrins are also included. This volume complements Volumes IV and V (Physical Chemistry, Parts Β and C), which cover resonance spectroscopies, Mössbauer spec- troscopy, redox chemistry, electron transport, and electrochemistry, as well as oxygenation, aggregation, and metallation of porphyrins and chlorophylls (including isolation and characterization) and their solid state phenomena. The final result is an up-to-date and critical review of the areas de- scribed above. This treatise provides, for the first time, a complete and comprehensive review of all of the major aspects of porphyrin chemistry and biochemistry. I wish to take this opportunity to thank the contributors to this volume. For those who completed their chapters on time, I give my thanks for their patience during the period between submission of their manuscript and the publication of this book. Of those who were not so prompt, I ask that they understand my impatience. DAVID DOLPHIN xiii Contents of Other Volumes VOLUME I STRUCTURE AND SYNTHESIS, PART A Chapter 1 Nomenclature R. Bonnett Chapter 2 Selected Landmarks in the History of Porphyrins and Their Biologically Functional Derivatives David L. Drabkin Chapter 3 Synthesis of Porphyrins from Monopyrroles Jean B. Kim, Alan D. Adler, and Frederick R. Longo Chapter 4 Synthesis of Pyrroles and of Porphyrins via Single-Step Coupling of Dipyrrolic Intermediates John B. Paine III Chapter 5 Synthesis of Porphyrins from 1,19-Dideoxybiladienes-tfc and l,19-Dideoxybilenes-& A. W. Johnson Chapter 6 Synthesis of Porphyrins from Oxobilane Intermediates P. S. Clezy and A. H. Jackson Chapter 7 Isolation and Modification of Natural Porphyrins Robert K. DiNello and C. K. Chang Chapter 8 TV-Substituted Porphyrins and Corroies A. H. Jackson Chapter 9 Azaporphyrins A. H. Jackson Chapter 10 Synthesis and Properties of Metalloporphyrins Johann Walter Buchler Chapter 11 Geochemistry of Porphyrins Earl W. Baker and Susan E. Palmer Chapter 12 Chromatography of Porphyrins and Metalloporphyrins William I. White, Robert C. Bachmann, and Bruce F. Burnham xv xvi CONTENTS OF OTHER VOLUMES Chapter 13 Nonchromatographic Methods of Purification of Porphyrins Veronica Varadi, Frederick R. Longo, and Alan D. Adler VOLUME II STRUCTURE AND SYNTHESIS, PART Β Chapter 1 Synthesis and Stereochemistry of Hydroporphyrins Hugo S che er Chapter 2 Hydroporphyrins: Reactivity, Spectroscopy, and Hydroporphyrin Analogues Hugo Scheer and Hans Herloff Inhoffen Chapter 3 The Porphyrinogens D. Mauzerall Chapter 4 Oxophlorins (Oxyporphyrins) P. S. Clezy Chapter 5 Irreversible Reactions on the Porphyrin Periphery (Excluding Oxidations, Reductions, and Photochemical Reactions) J.-H. Fuhrhop Chapter 6 Chemical Transformations Involving Photoexcited Porphyrins and Metalloporphyrins Frederick R. Hopf and David G. Whit te η Chapter 7 Linear Polypyrrolic Compounds Albert Gossauer and Jürgen Engel Chapter 8 Metal Complexes of Open-Chain Tetrapyrrole Pigments J. Subramanian and J.-H. Fuhrhop Chapter 9 Stereochemistry and Absolute Configuration of Chlorophylls and Linear Tetrapyrroles Hans Brockmann, Jr. Chapter 10 Pyrrolic Macrocycles Other than Porphyrins R. G rig g VOLUME IV PHYSICAL CHEMISTRY, PART Β Chapter 1 NMR Spectra of Diamagnetic Porphyrins Thomas R. Janson and Joseph J. Katz Chapter 2 NMR of Paramagnetic Porphyrins Gerd Ν. La Mar and F. Ann Walker Chapter 3 ENDOR Spectroscopy of the Chlorophylls and the Photosynthetic Light Conversion Apparatus James R. Nor ris, Hugo Scheer, and Joseph J. Katz Chapter 4 ESR of Porphyrin π Cations and Anions J. Fajer and M. S. Davis Chapter 5 Electron Spin Resonance of Porphyrin Excited States J. H. van der Waals, W. G. van Dorp, and T. J. Schaafsma Chapter 6 Electron Paramagnetic Resonance of Hemoproteins Graham Palmer