) ) ) l ' 1 I ) Inorganic Chemistry Principles of Structure and ) ( Reactivity t ( Fourth Edition ) (J I. ) ) James E. Huheey University of ,Haryland Ellen A. Keiter Eastern Illinois Unh•ersity ( Richard L. Keiter Eastern Illinois Univer.l'it_v u u l \..) C) ~_) \) :: HarperCollinsCollegePublishers [ l To Catherine, Cathy. Terry, Mercedes, Thorjin, Irene, A/vi,;, Eric, and Lise. Figures from the following journals are copyright @ to the American Chemical Society: AccoutJts of Chemi<:al Research. Chemical and Engineering Nrws, Chemical Reviews, Inorganic Chemistry, Journal of the American Chemical Society, Journal of Chemical Education, Journal of Physical Chemistry, and Organometallics. Grateful acknowledgment is also given to Acta Chemict1 Scandinavica, The American Association for the Advancement of Science, The American lnstitule of Physics. Angewtmdte Chemie, The Chemical Society, The International Union of Crystallography, The Mineralogical Society of America, The National Academy of Sciences, U.S.A., Nature, The Nobel Foundation of the Royal Academy of Science, Sweden, Zeitschrift flir anorgani.'C'he und allgemeine Chemie. and Zeitschrift fl'ir Naturforschung for the use of materials that are copyright <!:! to them. Individual acknowledgments are given on the pages where the material occurs. About the Cover The crystal structure of boggsite, a recently discovered natural zeolite, is composed of sodium, calcium, aluminum. silicon. hydrogen. and oxygen. Its unique atomic structure of ten and twelve rings was determined by J. J. Pluth and J. V. Smith, geophysicists at the University of Chicago. Modeling tools used to construct the cover photograph are being developed in the Catalysis and Sorption Project of BIOSYM Technologies, Inc., San Diego, California. Structure of boggsite counesy of Pluth. J. J.; Smith, J. V. Am. Mineral. J990, 75, 501-507, and computer graphic by John M. Newsam. BIOSYM Technologies, Inc. Sponsoring Editor: Jane Piro Project Coordination: Elm S1rcet Publishing Services, Inc. Cover Design: Kay Fulton Cover Photo: Professor John M. Newsam, BJOSYM Technologies, Inc. Compositor: Better Graphics, Inc. Printer and Binder: R. R. Donnelley & Sons Company Cover Printer: Lehigh Press Lithographers /lwrganic Chemisrry: Principles of Structure and Reactivity, Founh Edition Copyright 0 1993 by HarperCollins College Publishers All rights reserved. Printed in the United States of America. No pan of this book may be used or reproduced in any manner whatsoever without written permission. except in the case of brief quollltions embodied in critical articles and reviews. For information address HarperCollins College Publishers. 10 East 53rd Street, New York. NY 10022. Library of Congress Cataloging-in-Publication Data Huheey, James E. Inorganic chemistry: principles of structure and reactivity I James E. Huheey, Ellen A. Keiter, Richard L. Keiter. p. em. Includes bibliographical references and index. ISBN 0-06-042995-X I. Chemistry, Inorganic. I. Keiter. Ellen A. II. Keiter, Richard L. Ill. Title. QD151.2.H84 1993 546-dc20 92-36083 97 98 99 12 11 10 9 Contents Preface xi To the Swdent xiv Excerpts from the Preface to the Third Editio11 xvi Chapter 1 What Is Inorganic Chemistry? Inorganic Chemistry. the Beginnings Inorganic Chemistry, an Example 2 Chemical Structure of Zeolites and Other Chemical Systems Chemical Reactivity 5 Conclusion 7 Chapter 2 The Structure of the Atom l 0 The Hydrogen Atom 10 The Polyelectronic Atom 20 Chapter 3 Symmetry and Group Theory 46 Symmetry Elements and Symmetry Operations 46 Point Groups and Molecular Symmetry 53 Irreducible Representations and Character Tables 59 Uses of Point Group Symmetry 6J Crystallogn1phy 74 v vi Contents Contents vii Chapter 4 Bonding Models in Inorganic Chemistry: 1. Ionic Compounds 92 Chapter 9 Acid-Base Chemistry 318 The Ionic Bond 92 Acid-Base Concepts 3 18 Lattice Energy 99 Measures of Acid-Base Strength 330 Size Effects 112 Hard and Soft Acids and Bases 344 The Predictive Power of Thermochemical Calculations on Ionic Compounds 127 Covalent Charact~r in Predominantly Ionic Bonds 129 Conclusion 134 Chapter 10 Chemistry in Aqueous and Nonaqueous Solvents 359 Water 360 Chapter 5 Bonding Models in Inorganic Chemistry: 2. The Covalent Nonaqueous Solvents 360 Bond 138 Molten Salts 374 Valence Bond Theory 139 Electrode Potentials and Electromotive Forces 378 Molecular Orbital Theory 1:53 Electronegativity 182 Chapter 11 Coordination Chemistry: Bonding, Spectra, and Magnetism 387 Bonding in Coordination Compounds 391 Chapter 6 The Structure and Reactivity of Molecules 203 Valence Bond Theory 391 The Structure of Molecules 203 Crystal Field Theory 394 Structure and Hybridization 220 Molecular Orbital Theory 413 Bond Lengths 232 Electronic Spectra of Complexes 433 Experimental Determination of Molecular Structure 233 Magnetic Properties of Complexes 459 Some Simple Reactions of Covalently Bonded Molecules 237 Chapter 7 The Solid State 252 Chapter 12 Coordination Chemistry: Structure 472 The Structures of Complex Solids 253 Coordination Number I 472 Imperfections in Crystals 263 Coordination Number 2 473 Conductivity in Ionic Solids 266 Coordination Number 3 474 ,. Solids Held Together by Covalent Bonding 269 Coordination Number 4 474 t Solid-State Materials with Polar Bonds 276 Coordination Number 5 479 } Coordination Number 6 488 Coordination Number 7 503 Coordination Number 8 507 Chapter 8 Chemical Forces 290 Higher Coordination Numbers 509 Internuclear Distances and Atomic Radii 290 Generalizations about Coordination Numbers 511 Types of Chemical Forces 296 Linkage Isomerism 513 Hydrogen Bonding 300 Other Types of Isomerism 521 Effects of Chemical Forces 307 The Chelate Effect 522 ., . .. Contents ix viii Contents \ 1 - \ Cages 785 ~· Chapter 13 Coordination Chemistry: Reactions, Kinetics, and Boron Cage Compounds 789 Mechanisms 537 Metal Clusters 807 Substitution Reactions in Square Planar Complexes 538 Conclusion 819 Thermodynamic and Kinetic Stability 547 Kinetics of Octahedral Substitution 548 Mechanisms of Redox Reactions 557 Chapter 17 The Chemistry of the Halogens and the Noble Gases 824 Noble Gas Chemistry 825 Chapter 14 Some Descriptive Chemistry of the Metals 577 Halogens in Positive Oxidation States 837 General Periodic Trends 578 Halides 848 Chemistry of the Various Oxidation States of Transition Metals 580 Pseudohalogens 852 Electrochemistry of the Halogens and Pscudohalogens 853 The Chemistry of Elements Potassium-Zinc: Comparison by Electron Configuration 582 The Chemistry of the Heavier Transition Metals 587 Oxidation States and EMFs of Groups 1-12 588 The Lanthanide and Actinide Elements 599 Chapter 18 Periodicity 857 Coordination Chemistry 608 First-and Second-Row Anomalies 858 The Transactinide Elements 613 The Use of p Orbitals in Pi Bonding 861 The Use (or Not) of d Orbitals by Nonmetals 866 Reactivity and d Orbital Participation 875 Chapter 15 Organometallic Chemistry 623 Periodic Anomalies of the Nonmetals and Posttransition Metals 876 The IS-Electron Rule 624 Metal Carbonyl Complexes 630 Nitrosyl Complexes 650 Dinitrogen Complexes 653 Chapter 19 The Inorganic Chemistry of Biological Systems 889 Metal Alkyls, Carbcnes, Carbynes, and Carbides 655 Energy Sources for Life 889 Nonaromatic Alkene and Alkyne Complexes 662 Metalloporphyrins and Respiration 891 Metallocenes 669 Dioxygen Binding, Transport, and Utilization 895 Reactions of Organometallic Complexes 686 Electron Transfer, Respiration, and Photosynthesis 911 Catalysis by Organometallic Compounds 705 Enzymes 919 Stereochemically Nonrigid Molecules 723 Nitrogen Fixation 933 Conclusion 730 The Biochemistry of Iron 935 Essential and Trace Elements in Biological Systems 941 Biochemistry of the Nonmetals 953 Chapter 16 Inorganic Chains, Rings, Cages, and Clusters 738 Medicinal Chemistry 954 Summary 960 Chains 738 Postscript 960 Rings 765 - - ..... .!_. - X Contents Appendix A The Literature of Inorganic Chemistry A-1 Appendix B Units and Conversion Factors A-3 Preface Appendix C Atomic States and Term Symbols A-7 Appendix D Character Tables A-13 Appendix E Bond Energies and Bond Lengths A-21 It has been twenty years since the senior author and Harper & Row, Publishers produced the first edition of Inorganic Chemistry: Pri11ciples of Srrucwre and Reac riviry. In that time: (a) The senior author has become 20 years more senior; (b) two new authors have joined the project; (c) Harper & Row, Publishers has become HarperCollins Publishers; and, most important, (d) inorganic chemistry has continued Appendix F An Overview of Standard Reduction Potentials of the to grow from its already lusty existence of two decades ago. It is becoming increas Elements A-35 ingly impossible for one person to monitor all areas of inorganic chemistry. The new authors bring to the book their interests in coordination chemistry, organometallics, and physical methods, as well as fresh viewpoints on a number of other topics. Nevertheless. the philosophy of the book remains unchanged: To bring to the reader Appendix G Tanabe-Sugano Diagrams A-38 the essentials of inorganic chemistry in an easily readable format with emphasis on the fact that inorganic chemistry is an exciting field of research rather than a closed body of knowledge. We three authors brought very different undergraduate experiences to the teach Appendix H Models, Stereochemistry, and the Use of Stereopsis A-40 ing of inorganic chemistry and the revision of this edition. One of us received a B.S. degree from a Ph.D. granting institution, one from a private non-Ph.D. liberal arts college, and one from a public non-Ph.D. liberal arts college. We have taught under graduate and graduate inorganic courses in a variety of settings. When we sat down to Appendix I The Rules of Inorganic Nomenclature A-46 discuss the revision, there were <t number of things that we agreed upon: (I) The book would be substantially updated. (2} The material presented would continue to be thoroughly referenced, and the references would continue to appear on the pages of Index A-78 interest. A relevant reference would not be omitted just because it had appeared in previous editions. (3) New illustrations, many from the original literature, would be added. (4} A greater selection of problems, many of them new, would be provided. Many problems would require library assistance, while others would cover the funda mental aspects of each topic. (5) A chapter on symmetry would be added. (6} Solid state chemistry would be given more emphasis. (7) The kinetics chapter would be more fully developed. (8} The descriptive and organometallic chemistry of the lan thanides and actinides would be included in the corresponding chapters for the transition metals. General consensus (among both authors and users) comes more easily than agreement on specifics. Our discussions of the symmetry chapter are a good example. All of us agTeed that the teaching of symmetry considerations at most institutions had xi I li xii Preface Preface xiii I ,l I for the most part been delegated to the inorganic chemists. But how much should be thank colleagues in departments that we have visited on sabbatical leaves: Fred taught, and how much should the remainder of the book depend upon this chapter'? At Hawthorne, Herb Kaesz, Charles Strouse, Joan Selverstone Valentine, and Jeff Zink l a minimum we believed that a good introduction to point groups was essential. We (University of California at Los Angeles). and Oren Anderson, Gary Maciel, Jack \ also wanted to include some character table applications but not so much that the Norton. Tony Rappe. and Steve Straus (Colorado State University). We would also ~ inorganic chemistry in the book couldn't be taught without it. Applications appear like to thank the Chemistry Departments at UCLA and CSU, the Zoology Department I here and there in the text but can be avoided if desired. The chapter, as completed, has at Southern Illinois University. as well as our own departments for making possible concentrated on familiarizing the student with many applications of symmetry as used sabbatical visits to take advantage of these resources. by the inorganic chemist, including spectroscopy and crystallography, without pur We are grateful 10 Michael W. Anderson. University of Cambridge; Anthony J porting to be a rigorous exposition of the subject. Arducngo. E. I. du Pont de Nemours; B. Dubost. Pechiney Institute; Jacek Klinow } We may anticipate an eventual consensus on the amount and place of symmetry in ski, University of Cambridge; John Newsam. BIOSYM Technologies; Joseph J. the chemistry curriculum, but for now we have assumed no prior background in the Pluth, University of Chicago; Arnold L. Rheingold. University of Delaware; subject. We have thus tried to illustrate a wide variety of uses of symmetry without P. Sainfort, Pechiney Institute; Charlotte L. Stem, University of Illinois, Urbana l delving deeply into the background theory. We hope that those new to the topic can Champaign; Sir John Meurig Thomas. The Royal Institution of Great Britain; and i find a useful introduction to the application of symmetry to problems in inorganic Scott Wilson. University of Illinois, Urbana-Champaign, for special help with illustra l chemistry. On the other hand, those having previous experience with the subject may tions from their work. wish to use this chapter as a brief review. And. recognizing that things are in a state of The writing of this text has benefitted from the helpful advice of many reviewers. ' flux, we have attempted to make it possible to study various topics such as orbital They include Ivan Bernal, Donald H. Berry, Patricia A. Bianconi, Andrew B. l overlap, crystal field theory, and related material, as in the past. with minimal Bocarsly, P. Michael Boorman, Jeremy Burdett. Ben DeGraff. Russell S. Drago, reference to symmetry if desired. Daniel C. Harris, Roald Hoffmann, Joel F. Liebman. John Milne, Terrance Murphy, Students using this book come from exceedingly diverse backgrounds: Some will Jack Pladziewicz. Philip Power, Arnold L. Rheingold. Richard Thompson. Glenn have had extensive experience in physical and organic chemistry. perhaps even a Vogel. Marc Walters. James H. Weber. and Jeff Zink. previous course in descriptive inorganic chemistry. For many, however. this will be We began this preface indicating "changes" that have occurred in the last two the first contact with inorganic chemistry, and some may have had only limited decades. We have dealt with new authorship and new inorganic chemistry above. experience with bonding theory in other courses. For this reason. the early chapters Concerning the merger of Harper & Row, Publishers. New York. and Collins. Pub present the fundamentals of atomic and molecular structure from the inorganic chem lishers. London. the entropy generated was quite unexpected. When the dust had ist's perspective. The well-prepared reader may use these chapters as a brief review as settled, there emerged two sterling performers: Jane Piro, Chemistry Editor. and Cate well as mortar to chink between previous blocks of knowledge. The middle chapters of Rzasa, Project Editor. who helped us in many ways. We are happy to acknowledge the book present the "heart of inorganic chemistry," solid-state chemistry beyond our debt to them. simple salts. acid-base chemistry in a variety of solvents and the gas phase. and Finally, there are many, many faculty and students who have helped in the coordination chemistry discussed in terms of bonding, spectra. magnetism, structure. original writing and further development of this book. often anonymous in the brief and reactions. citation of colleagues and reviewers. They know who they are, and we hope they will In line with the philosophy of a topical approach and flexible course content, the accept our sincere thanks for all that they did. last six chapters of the book are essentially independent of each other, and one or more may readily be omitted depending on the inclination of the instructor and the James E. Huheey time available. Ellen A. Keiter The fourth edition, in its entirety, works nicely for that unfortunately rare beast. Richard L. Keiter the two-semester course. But that means that it is balanced and should work equally well for a one-semester course- the instructor must pick and choose. We firmly believe that it is more useful to provide a large number of topics, wherein one can select the topics lobe covered, than to dictate a "minimum core." We hope the book includes the topics that all instructors find essential. but we hope that it also includes their favorite topics. It obviously tncludes ours. A solutions manual that contains answers to all end-of-chapter problems nccompanies the fourth edition. We would like to thank our colleague> at the University of Maryland at College Park (UMCP) and Eastern Illinois University (EIU) who have helped in a multllude of ways. Professor Huhecy's colleagues who helped with previous editions are listed in the "Excerpts from the Preface to the Third Edition" (page xvi). and their further help is gratefully acknowledged. In addition. we would like to thank Bryan Eichhorn (UMCP), William Harwood (UMCP). Mark McGuire (EIU). Robert Pilato (UMCP), and Rinaldo Poli (UMCP) for special help with this edition. We would also like to To the Student xv limiting each topic to a few paragraphs. This has the adv;mtage of including most topics but the disadvantage of having to look elsewhere for a fuller development. Any single book, of course. has this problem to a certain degree, thus the need for m~ny references. Our book, Inorganic Chemistry: Principles of Strucl/lre and ReactiVIty, fourth edition. is also a blend of fact and theory, but we think it is large enough for a full meal. There is no reason to expect a book that deals with the chemistry of 109 elements to be smaller than a standard organic chemistry textbook! To the Student We've enjoyed writing this book; we hope that you will enjoy reading it. lf you do, we'd like to hear from you. James E. Huheey Ellen A. Keiter Richard L. Keiter Once after a departmenta.J seminar, an older professor was heard to remark lhat he fell intimidated by all of the new theory and experimental spectroscopic methods known by the new chemistry graduates. A young graduate student was stunned: she was sure it would take her years just to Jearn enough of the chemistry that he already knew to get her degree. Meanwhile, two other professors were arguing heatedly over the relative importance of facts versus theory. One said descriptive chemistry was the most important because "facts don't change!'' "Well, some 'facts' seem to change- I read yesterday that iridium is the densest element: ten years ago when I was a student, I was told that osmium was the densest." "They don't change as fast as theories; theories just come and go; besides, what's wrong with someone repeating an experiment and doing it beuer-gelling a more accurate value?" "That's the point; new theories are necessary to explain new experimental data, and theories give us something to test, a framework around which we can dream ..." "Dream! We need a lillie less 'inspiration' and a lot more perspiration ... " And so it goes .. .. These chemists and these arguments present a microcosm of perpetual debates in chemistry and the essence of the great difficulty in writing an upper level textbook of inorganic chemistry. The field is vast: large numbers of inorganic articles are published every week. New synthetic techniques allow the isolation and identification of great numbers of highly reactive compounds. The oretical descriptions have become increasingly sophisticated. as have spectroscopic methods. Inorganic chemistry interacts with organic. physical, and even biological chemistry. Borderlines between molecular and solid-state chemistry are rapidly disap pearing. The older chemist may know many facts and theories but realizes it is only a small portion of the whole. The new graduate, with well-developed skills in a few areas, also has a sense of inadequacy. Perhaps the student faced with his or her first advanced inorganic course feels this most acutely. The textbook for the course reOects the instructor's choice of what portion of inorganic chemistry should be taught, what mix of facts and theory. and what relative weight of traditional and new science. Authors also make their choices and those are seen in the variety of available textbooks on the market. Some are heavily factual, usually bulky, and especially useful for finding out something about all of the principal compounds of a particular xiv element. Others present a blend of fact and theory but minimize the book bulk by