METAL-LIGAND INTERACTIONS IN ORGANIC CHEMISTRY AND BIOCHEMISTRY PART 1 THE JERUSALEM SYMPOSIA ON QUANTUM CHEMISTRY AND BIOCHEMISTRY Published by the Israel Academy of Sciences and Humanities. distributed by Academic Press (N. Y.) 1st JERUSALEM SYMPOSIUM: The Physicochemical Aspects of Carcinogenesis (October 1968) 2nd JERUSALEM SYMPOSIUM: Quantum Aspects of Heterocyclic Compounds in Chemistry and Biochemistry (April 1969) 3rd JERUSALEM SYMPOSIUM: Aromaticity. Pseudo-Aromaticity. Antiaromaticity (April 1970) 4th JERUSALEM SYMPOSIUM: The Purines: Theory and Experiment (April 1971) 5th JERUSALEM SYMPOSIUM: The Conformation of Biological Molecules and Polymers (April 1972) Published by the Israel Academy of Sciences and Humanities. distributed by D. Reidel Publishing Company (Dordrecht and Boston) 6th JERUSALEM SYMPOSIUM: Chemical and Biochemical Reactivity (April 1973) Published and distributed by D. Reidel Publishing Company (Dordrecht and Boston) 7th JERUSALEM SYMPOSIUM: Molecular and Quantum Pharmacology (MarchiA pril 1974) 8th JERUSALEM SYMPOSIUM: Environmental Effects on Molecular Structure and Properties (April 1975) VOLUME 9 METAL-LIGAND INTERACTIONS IN ORGANIC CHEMISTRY AND BIOCHEMISTRY PART 1 PROCEEDINGS OF THE NINTH JERUSALEM SYMPOSIUM ON QUANTUM CHEMISTRY AND BIOCHEMISTRY HELD IN JERUSALEM, MARCH 29TH-APRIL 2ND, 1976 Edited by BERNARD PULLMAN Institut de Biologie Physico-Chimique (Fondation Edmond de Rothschild) Paris, France and NATAN GOLDBLUM The Hebrew University, Hadassah Medical School, Jerusalem, Israel D. REIDEL PUBLISHING COMPANY DORDRECHT-HOLLAND/BOSTON-U.S.A. Library of Congress Cataloging in Publication Data Jerusalem Symposium on Quantum Chemistry and Biochemistry, 9th, 1976. Metal-ligand interactions in organic chemistry and biochemistry. (The Jerusalem symposia on quantitative chemistry and biochemistry; v. 9) Bibliography: p. Includes index. \. Ligands-Congresses. 2. Chemistry, Organic-Congresses. 3. Biological chemistry-Congresses. I. Pullman, Bernard, 1919- II. Goldblum, Natan. III. Title. IV. Series. QD474.J47 1976 547' .\'2242 76-44910 The set of two parts: ISBN 90-277-0771-5 ISBN-13: 978-94-010-1172-3 e-ISBN-13: 978-94-010-1170-9 001: 10. 1007/978-94-010-1170-9 Published by D. Reidel Publishing Company, P.O. Box 17, Dordrecht, Holland Sold and distributed in the U.S.A., Canada, and Mexico by D. Reidel Publishing Company, Inc. Lincoln Building, 160 Old Derby Street, Hingham, Mass. 02043, U.S.A. All Rights Reserved Copyright © 1977 by D. Reidel Publishing Company, Dordrecht, Holland Softcover reprint of the hardcover 1s t edition 1977 No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying, recording or by any informational storage and retrieval system, without written permission from the copyright owner TABLE OF CONTENTS TABLE OF CONTENTS OF PART 2 VII PREFACE IX A. PULLMAN/Search for General Features in Cation-Ligand Binding. Ab initio. SCF Studies of the Interaction of Alkali and Alkaline Earth Ions with Water T.J. KISTENMACHER and L.G. MARZILLI/Chelate Metal Complexes of Purines, Pyrimidines and Their Nucleosides: Metal-Ligand and Ligand-Ligand Interactions 7 G.L. EICHHORN, J. RIFKIND, Y.A. SHIN, J. PITHA, J. BUTZOW, P. CLARK, and J. FROEHLICH/Recent Studies on the Effects of Divalent Metal Ions on the S'tructure and Function of Nucleic Acids 41 E. SLETTEN/Crystallographic Studies on Copper Complexes of Nu- cleic Acid Components 53 B. PULLMAN and A. PULLMAN/Quantum-Mechanical Studies on Cation Binding to Constituents of Nucleic Acids and Phospholipids 65 S. HANLON, B. WOLF, S. BERMAN, and A. CHAN/The Conformational Sensitivity of DNA to Ionic Interactions in Aqueous Solu- tions 77 G.V. FAZAKERLEY, G.E. JACKSON, J.C. RUSSELL, and M.A. WOLFE/ Interaction of Gadolinium (III), Manganese (II) and Copper (II) with Cyclic Nucleotides 107 W. LOHMANN, A. PLEYER, M. HILLERBRAND, V. PENKA, K. G. WAGNER, and H.A. ARFMANN/lnfluence of Heterocyclic Nitrogen Atoms on the Interaction between Purine Analogues and Metal Ions 115 B.M. RODE/The Investigation of Metal-Amide Interactions with the Aid of Quantum Chemical Model Calculations and Corre- sponding Model Experiments 127 C.N.R. RAO/lnteraction of Alkali and Alkaline Earth Cations and Protons with Amides and Related Systems 147 D. BALASUBRAMANIAN and B.C. MISRA/Alkali Ion Binding to Poly- peptides and Polyamides 159 M.H. BARON, H. JAESCHKE, R.M. MORAVIE, C. de LOZE, and J. COR SET/Infrared and Raman Studies of Interactions between Salts and Amides or Esters 171 B. SARKAR/Concept of Molecular Design in Relation to the Metal- Binding Sites of Proteins and Enzymes 193 L.H. JENSEN/Metal Complexes in Proteins 229 G. ROTILIO, L. MORPURGO, L. CALABRESE, A.F. AGRO, and B. MON- DOV1/Metal-Ligand Interactions in Cu-Proteins 243 VI Table of Contents C.M. DOBSON and R.J.P. WILLIAMS/Nuclear Hagnetic Resonance Studies of the Interaction of Lanthanide Cations with Lysozyme 255 M.M. WERBER, A. DANCHIN, Y. HOCHMAN, C. CARMELI, and A. LANIR/ Co(III1-ATP Complexes as Affinity Labeling Reagents of Hyosin and Coupling Factor-l ATPases 283 G.D. SMITH and W.L. DUAX/Crystallographic Studies of Valino- mycin and A23187 291 H.R. TRUTER/Effects of Cations of Groups IA and IIA on Crown Ethers 317 R.M. IZATT, L.D. HANSEN, D.J. EATOUGH, J.S. BRADSHAW, and J.J. CHRISTENSEN/Cation Selectivities Shown by Cyclic Polyethers and Their THIA Derivatives 337 W. SAENGER, H. BRAND, F. VOGTLE, and E. WEBER/ X-Ray Structure of a Synthetic, Non-Cyclic, Chiral Polyether Complex as Analog of Nigericin Antibiotics: Tetraethyleneglycol-bis (8-oxyquinoline)-ether . rubidium Iodide Complex 363 J.J. STEZOWSKI/Metal Ion - Ligand Interactions for the Tetra- cycline Derivative Antibiotics: a Structural Approach 375 TABLE OF CONTENTS OF PART 2 G. EISENMAN, J. SANDBLOM, and E. NEHER/Ionic Selectivity, Satu ration, Binding, and Block in the Gramicidin A Channel: A Preliminary Report A.P. THOMA and W. SIMON/Enantiomer-Selective Ion Carriers and Their Transport Properties in Bulk Membranes L.K. STEINRAUF and M.N. SABESAN/Computer Simulation Studies on the Ion-Transporting Antibiotics J. OTSUKA, Y. SENO, N. FUCHlKAMI, and o. MATSUOKA/Theoretical Calculation on Oxygen Binding to the Heme Iron in Myoglobin and Hemoglobin A. DEDIEU, M.-M. ROHMER, and A. VEILLARD/Oxygen Binding to Iron Porphyrins. Ab initio Calculations W.S. CAUGHEY, J.C. MAXWELL, J.M. THOMAS, D.H. O'KEEFFE, and W.J. WALLACE/Metal-Ligand Interactions in Porphyrins and Hemeproteins M. CHEVION, W.E. BLUMBERG, and J. PEISACH/EPR Studies of Human Nitrosyl Hemoglobins and Their Relation to Molecular Func tion R. BANERJEE, J.M. LHOSTE, and F. STETZKOWSKI/Carbon-13 NMR Studies of Human Hemoglobin and Some Other Hemoproteins K.B. WARD and W.A. HENDRICKSON/Structures of the Non-heme Iron Proteins Myohemerythrin and Hemerythrin D.H. HAYNES/Divalent Cation-Ligand Interactions of Phospholipid Membranes: Equilibria and Kinetics T.O. HENDERSON/31p Nuclear Magnetic "Resonance Studies of Metal Ligand Interactions in Human Blood Components W.J. COOK and C.E. BUGG/Structures of Calcium-Carbohydrate Complexes R.H. KRETSINGER/Why Does Calcium Play an Informational Role Unique in Biological Systems? G. ZUNDEL and A. MURR/lnfluence of Transition Element Ions on the Hydrogen Bonds Formed by Their First Hydration Shell M.A. WELLS and T.C. BRUICE/The Nucleophilicity of Metal Bound Hydroxide, Mechanisms of Displacement on Esters, and Transesterification Involving the Metal-Acyl Anhydride Bond J. JAGUR-GRODZINSKI and Y. OZARI/Complexes of Cobalt with Poly meric Phosphoramides J. KRESS, C. SOURISSEAU, and A. NOVAK/Infrared and Raman Studies of Some Organomagnesium and Allyl Compounds B. BIRDSALL, J. FEENEY, and A.M. GUILIANI/Conformational Studies of Flexible Molecules Using Lanthanide Ions as NMR Probes VIII TabZe of Contents of Part 2 J. REUBEN/Metal Ions as Probes for NMR Studies of Structure and Dynamics in Systems of Biological Interest G.H.F. DIERCKSEN and W.P. KRAEMER/SCF MO LOGO Studies on Elec trolytic Dissociation: the System LiF.nH20 (n=1,2) B. AKERMARK, M. ALMEMAP.K, J .-E. BACKVALL, J. ALMLOF, B. ROOS, A. and ST¢GARo/Ab initio Calculations on Nickel-Ethylene Complexes H. BASCH/Metal-Ligand Interactions and Photoelectron Spectro scopy PREFACE The 9th Jerusalem Symposium was dedicated to the memory of Professor Ernst David Bergmann. An imposing and deeply moving memorial session, chaired by Professor Ephraim Katzir, the President of the State of Is rael and a close friend of Professor Bergmann preceded the Symposium itself. During this session, Professor Bergmann's personality, scien tific achievements and contributions to the development of his country were described and praised, besides President Katzir, by Professor A. Dvoretzky, President of the Israel Academy of Sciences and Humanities, Professor D. Ginsburg, Dean of the Israel Institute of Technology in Haifa and the author of these lines. May I just quote short extracts from these speeches. President Katzir: "As we open this ninth in the series of symposia initiated in 1967, it is difficult for me as, I am sure, for many of Ernst Bergmann's friends, co-workers and students, to be here without him. He was not only a great scientist and a beloved teacher, he was one of the most important founders of science in this country. To him we owe many institutes and the establishment here of many branches of science." Professor Dvoretzky: "Ernst Bergmann's greatness did not stem from one component overshadowing all the others. It was a multifaceted great ness consisting of the harmonious co~lescing of seemingly contrasting entities into a wonderful unity ••. A deep universality dwelt in him jointly and in full harmony with an ardent love for his people and na tion. A deep respect for tradition and the heritage of the past, with an admiration for progress and innovation. A faultless memory, with originality. Bold initiative, with prudent sagacity. Great were his achievements and no less great the achievements which he inspired oth ers to make. He headed great projects, but he was equally ready to lend active support to any project, no matter how small, which he con sidered deserving. His approach to public affairs was always imperson al and guided by sober analysis; yet he displayed a wonderful warmth in his personal contacts. He was most demanding of himself and under standing towards his fellow men." Professor Ginsburg: "It is not possible to encompass in a short ses sion or even to attempt to do just-ice to the accomplishments of the phenomenon named Ernst David Bergmann. Those of you who did not know him should know, after all has been said and done, that the whole was more than the sum of the descriptions." x Preface May I also quote from my own speech: "I do not know any other man like Ernst. None, whose knowledge and wisdom, simplicity and depth, devo tion to science and love of his country, were comparable to his. He was a unique combination of all these elements fused together by an exceptional human warmth, which irresistibly conquered all those who had the priviledge of approaching him and knowing him ... I believe that during the last years of his life, the preparation, organization and yearly holding of the Jerusalem Symposia were for Ernst one of his preferred tasks. I also believe that this task was a joyful and pleas ant one, although a hard one, for him. Just as he always did, in all his scientific works, he paid the utmost attention and attached the utmost importance to the perfection of the organization. He looked af ter all the details himself, always searching to improve, caring for everybody's satisfaction and pleasure. I know also, that the success and the growing renown of these Symposia were a great joy to him." I wish once more to express my deep thanks to all those who in one way or another contribute to the possibility and success of the Jerusalem Symposia. Our deepest thanks are due to the Baron Edmond de Rothschild whose understanding and generosity make these Symposia possible and to the Israel Academy of Sciences and Humanities, and the Hebrew Univer sity of Jerusalem for their support, and collaboration. BERNARD PULLMAN