Inorganic chemistry : principles of structure and reactivity

529 Pages·1993·141.24 MB·English

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Inorganic Chemistry
Principles of
Structure and
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Reactivity
t
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) Fourth Editi on
(J
I. )
) James E. Huheey
University of ,Haryland
Ellen A. Keiter
Eastern Illinois Unh•ersity
( Richard L. Keiter
Eastern Illinois Univer.l'it_v
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[ l :: HarperCollinsCollegePublishers
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 A cta Chemict1 Scandinavica, The American
Association for the Advancement of Science, T he 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 c rystal structure of boggsite, a recently discovered natural zeolite, is composed of
sodium, calcium, aluminum. si licon. hydrogen. and oxygen. Its unique a tomic 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
Techno logies, Inc.
Sponsoring Editor: Jane Piro
Projec t 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 HarperColl ins 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
Crystal logn1phy 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 11 2
Hard and Soft Acids and Bases 344
The Predic tive 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 39 1
The Struc ture 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 Dis tances and Atomic Radii 290
Generalizations about Coordination Numbers 5 11
Types of Chemical Forces 296
Linkage Isomerism 513
Hydrogen Bonding 300
Other T ypes of Isomerism 52 1
Effects of Chemical Forces 307
The Chelate Effec t 522
., . ..
Conte nts ix
1
\ viii C o nte nts - \
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 Ox idation States of Transition Metals 580 Pseudohalogens 852
The Chemis try of Elements Potassium-Zinc: Comparison by Electron E lectrochemistry of the Halogens and Pscudohalogens 853
Configuration 582
The Chemistry of the Heavier Transition Metals 587
Oxidation Sta tes and EMFs of Groups 1- 12 588
The La nthanide and Actinide Elements 599 Chapter 18 Periodicity 857
Coordination Chemistry 608 First- and Second-Row Anomalies 858
The Transactinide Elements 6 13 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 a nd 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
Nona romatic Alkene and Alkyne Complexes 662 Metalloporphyrins and Respiration 89 1
Metallocenes 669 Dioxygen Binding, Transport, and Utilization 895
Reactions of Organometallic Complexes 686 Electron T ransfer , Respiration, and Photosynthesis 9 11
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 Chemist ry 954
Summary 960
Chains 738
Postscript 960
Rings 765
- ..... .!_. -
-
X Conte nts
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
It has been twent y years since the senior author and Harper & Row, Publishers
Appendix E Bond Energies and Bond Lengths A-21
produced the fi rst 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 bri ng 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
fac t that inorganic chemistry is a n 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 varie ty 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 upo n: ( I ) The book
would be substantiall y updated. (2} The material presented would continue to be
thoroughly referenced, and the references would continue to appear on the pages of
interest. A relevant reference would not be omitted just because it had appeared in
Index A-78
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 requ ire library assistance, while others would cover the funda-
mental aspects of each topic . (5) A chapter on symmetry would be added. (6} Solid
state chemis try would be given more emphasis. (7) The kinetics chapter would be
more fully developed. (8} The descri ptive and organometa llic chemistry of the lan-
thanides and actinides would be included in the corresponding chapters fo r 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 considera tions at most institutions had
xi
I
Il i xii Preface Preface xiii
,l
for the most part been delegated to the inorganic chemists. But how much should be thank colleagues in departments tha t we have visited on sabbatical leaves: Fred
I taught , and how much should the remainder of the book depend upon this chapter'? At Hawthorne , Herb Kaesz, Cha rles Strouse, Joan Selvers tone Valentine , and Jeff Zink
l a minimum we believed that a good introduction to point groups was essentia l. We (Universi ty 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 S teve Straus (Colorado Sta te University). We would also
I~ ihneorerg aanndic t hcehreem inis thrye tienx t hbeu tb coaonk bceo auvldonid'te db ief dtaeusigrhetd .w Tithheo cuht aipt.t eAr,p apsl iccoamtiopnles teadp,p heaasr alitk eS otou tthearnnk Itlhlien Coihs eUmnisitvreyr sDiteyp. aartsm weenltls aast oUuCr LoAw na ndde pCaSrtUm, ethntes Zfooor lmogayk iDngep paortsmsiebnlet
concentrated on familiarizing the student with many applications of symmetry as used sabbatical visits to take advantage of these resources.
by t he inorganic chemis t , inc luding 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 subjec t. Arducngo. E. I. du Pont de N emours; 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 chemis try 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 ; C harlotte L . Stem , University of Illinois, Urbana-
il dfiendlv ian gu dseefupl lyin itnrtood uthcet iobna ctkog rtohuen adp tphliecoartyio. nW oef h soypme mtheattry t htoos ep rnoebwle mtos t hine tionopricg acnaicn CSchoatmt pWaiilgsno;n .S Uir nJiovhenrs iMtye oufr iIgll iTnohiosm, Uasr.b aTnhae- CRhoaymapl aIingsnt,i tfuotri osnp eocfi aGl hrealpt wBirtihta iilnlu; satrnad-
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 s tate 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.
overlap, c rystal field theory, and related materia l, 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 Hoffma nn , Joel F . Liebman . John Milne, Terrance Murphy ,
Students using this book come from exceedingly di verse backgrounds: Some will Jack Pladziewicz. Philip Power, Arnold L. Rheingold. Richard Thompson. Glenn
l have had extensive experience in physical and organic chemistry. perhaps even a Vogel. Marc Walters. James H. Weber. and Jeff Zi nk.
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 fi rst 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- lishe rs. 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 s terling performers: Jane Piro , Chemistry Editor. and Cate
well as mortar to chink between previous blocks of knowledge. The middle c hapters of Rzasa, Project Editor. who he lped us in man y ways. We are happy to acknowledge
the book present the " heart of inorganic chemis try," 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, man y faculty a nd stude nts 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 fle xible course content, the accept our sincere thanks for a ll that they did.
last s ix chapters of the book are essentiall y independent of each o ther, and one or
more may readily be omitted depending on the inclination of the ins tructor and the James E. Huheey
time available. Ellen A. Keiter
The fourth edition, in its entirety , works nicel y for that unfortuna tely 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 obvious ly tncludes ours. A solutions manual that contains
answers to all end-of-chapte r problems nccompanies the fourth edition.
We would like to thank our colleague> at the Univers ity of Maryland at College
Park (UMCP) and Eas tern Illinois Universit y (E IU) who have he lped 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). Ma rk 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 fu ller 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
e lements 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 c hange- 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 c hemistry 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 a llow the
isolation and identification of great numbers of highly reactive compounds. The-
oretical descriptions have become increasingly sophisticated. as have spectroscopic
methods. Inorganic che mistry 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 s tudent faced with his or her first
advanced inorganic course feel s 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 fac ts a nd theory. a nd 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 fact ual, 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