Inorganic Chemistry

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 Inorganic Chemistry
Second Edition

James E. House
Illinois Wesleyan University
and Illinois State University

AMSTERDAM  BOSTON  HEIDELBERG  LONDON  NEW YORK  OXFORD

PARIS  SAN DIEGO  SAN FRANCISCO  SINGAPORE  SYDNEY  TOKYO
Academic Press is Imprint of Elsevier
Elsevier
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First edition 2008
Second edition 2013
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Library of Congress Cataloging-in-Publication Data
A catalog record for this book is available from the Library of Congress
Library of Congress Cataloging-in-Publication Data
House, J. E.
Inorganic chemistry / James House. e 2nd ed.
p. cm.
Includes bibliographical references and index.
1. Chemistry, Inorganic e Textbooks. I. Title.
QD151.5.H68 2013
546–dc23
2012017867
ISBN: 978-0-12-385110-9

For information on all Elsevier publications

visit our website at www.store.elsevier.com

Printed and bound in China

12 13 11 10 9 8 7 6 5 4 3 2
Contents

PREFACE TO THE SECOND EDITION............................................................................................xi

PREFACE TO THE FIRST EDITION................................................................................................xii

PART 1 Structure of Atoms and Molecules ....................................................... 1

CHAPTER 1 Light, Electrons, and Nuclei ...................................................................................... 3
1.1 Some Early Experiments in Atomic Physics ................................................................... 3
1.2 The Nature of Light ........................................................................................................... 7
1.3 The Bohr Model................................................................................................................ 11
1.4 ParticleeWave Duality..................................................................................................... 14
1.5 Electronic Properties of Atoms....................................................................................... 16
1.6 Nuclear Binding Energy .................................................................................................. 21
1.7 Nuclear Stability ............................................................................................................... 23
1.8 Types of Nuclear Decay .................................................................................................. 25
1.9 Predicting Decay Modes ................................................................................................. 28

CHAPTER 2 Basic Quantum Mechanics and Atomic Structure ................................................33

2.1 The Postulates.................................................................................................................. 33
2.2 The Hydrogen Atom ........................................................................................................ 40
2.3 The Helium Atom............................................................................................................. 45
2.4 Slater Wave Functions..................................................................................................... 47
2.5 Electron Configurations .................................................................................................. 49
2.6 Spectroscopic States ........................................................................................................ 54

CHAPTER 3 Covalent Bonding in Diatomic Molecules ..............................................................61

3.1 The Basic Ideas of Molecular Orbital Methods ............................................................ 61
3.2 The Hþ2 and H2 Molecules ............................................................................................... 69
3.3 Diatomic Molecules of Second-Row Elements.............................................................. 71
3.4 Photoelectron Spectroscopy............................................................................................ 77
3.5 Heteronuclear Diatomic Molecules ................................................................................ 79
3.6 Electronegativity .............................................................................................................. 82
3.7 Spectroscopic States for Molecules................................................................................ 85

v
vi Contents

CHAPTER 4 A Survey of Inorganic Structures and Bonding..................................................... 89

4.1 Structures of Molecules Having Single Bonds.............................................................. 89
4.2 Resonance and Formal Charge ...................................................................................... 99
4.3 Complex Structures: A Preview of Coming Attractions ........................................... 111
4.4 Electron-Deficient Molecules ........................................................................................ 119
4.5 Structures Having Unsaturated Rings......................................................................... 121
4.6 Bond Energies ................................................................................................................ 123

CHAPTER 5 Symmetry and Molecular Orbitals ........................................................................129

5.1 Symmetry Elements....................................................................................................... 129
5.2 Orbital Symmetry ........................................................................................................... 137
5.3 A Brief Look at Group Theory ...................................................................................... 139
5.4 Construction of Molecular Orbitals.............................................................................. 144
5.5 Orbitals and Angles ....................................................................................................... 150
5.6 Simple Calculations Using the Hückel Method .......................................................... 152

PART 2 Condensed Phases............................................................................... 167

CHAPTER 6 Dipole Moments and Intermolecular Interactions...............................................169
6.1 Dipole Moments ............................................................................................................. 169
6.2 DipoleeDipole Forces .................................................................................................... 174
6.3 Dipole-Induced Dipole Forces....................................................................................... 176
6.4 London (Dispersion) Forces .......................................................................................... 177
6.5 The van der Waals Equation ........................................................................................ 181
6.6 Hydrogen Bonding ......................................................................................................... 183
6.7 Cohesion Energy and Solubility Parameters .............................................................. 192
6.8 Solvatochromism ............................................................................................................ 196

CHAPTER 7 Ionic Bonding and Structures of Solids ................................................................201

7.1 Energetics of Crystal Formation ................................................................................ 201
7.2 Madelung Constants ................................................................................................... 205
7.3 The Kapustinskii Equation ......................................................................................... 209
7.4 Ionic Sizes and Crystal Environments....................................................................... 210
7.5 Crystal Structures ........................................................................................................ 213
7.6 Solubility of Ionic Compounds.................................................................................... 219
7.7 Proton and Electron Affinities .................................................................................... 224
7.8 Structures of Metals..................................................................................................... 227
7.9 Defects in Crystals ....................................................................................................... 230
7.10 Phase Transitions in Solids......................................................................................... 233
7.11 Heat Capacity ............................................................................................................... 234
7.12 Hardness of Solids ....................................................................................................... 237
 Contents vii

CHAPTER 8 Dynamic Processes in Inorganic Solids ................................................................243

8.1 Characteristics of Solid-State Reactions.................................................................... 243
8.2 Kinetic Models for Reactions in Solids ...................................................................... 245
8.3 Thermal Methods of Analysis .................................................................................... 253
8.4 Effects of Pressure ....................................................................................................... 254
8.5 Reactions in Some Solid Inorganic Compounds ....................................................... 256
8.6 Phase Transitions ........................................................................................................ 258
8.7 Reactions at Interfaces................................................................................................ 262
8.8 Diffusion in Solids ........................................................................................................ 263
8.9 Sintering ........................................................................................................................ 265
8.10 Drift and Conductivity ................................................................................................. 267

PART 3 Acids, Bases, and Solvents ................................................................ 271

CHAPTER 9 AcideBase Chemistry ............................................................................................273
9.1 Arrhenius Theory......................................................................................................... 273
9.2 BrønstedeLowry Theory............................................................................................. 276
9.3 Factors Affecting the Strength of Acids and Bases................................................. 279
9.4 AcideBase Character of Oxides................................................................................. 284
9.5 Proton Affinities ........................................................................................................... 286
9.6 Lewis Theory................................................................................................................ 288
9.7 Catalytic Behavior of Acids and Bases...................................................................... 292
9.8 The HardeSoft Interaction Principle (HSIP).............................................................. 296
9.9 Electronic Polarizabilities............................................................................................ 305
9.10 The Drago Four-Parameter Equation......................................................................... 306

CHAPTER 10 Chemistry in Nonaqueous Solvents....................................................................313

10.1 Some Common Nonaqueous Solvents..................................................................... 313
10.2 The Solvent Concept ................................................................................................. 314
10.3 Amphoteric Behavior................................................................................................. 316
10.4 The Coordination Model ........................................................................................... 317
10.5 Chemistry in Liquid Ammonia ................................................................................. 318
10.6 Liquid Hydrogen Fluoride......................................................................................... 324
10.7 Liquid Sulfur Dioxide................................................................................................. 326
10.8 Superacids .................................................................................................................. 330

PART 4 Chemistry of the Elements ................................................................ 335

CHAPTER 11 Chemistry of Metallic Elements ..........................................................................337
11.1 The Metallic Elements ............................................................................................ 337
11.2 Band Theory ............................................................................................................. 338
viii Contents

11.3 Groups IA and IIA Metals....................................................................................... 341

11.4 Zintl Phases .............................................................................................................. 349
11.5 Aluminum and Beryllium........................................................................................ 351
11.6 The First-Row Transition Metals........................................................................... 353
11.7 Second- and Third-Row Transition Metals........................................................... 355
11.8 Alloys......................................................................................................................... 357
11.9 Chemistry of Transition Metals ............................................................................. 360
11.10 The Lanthanides ...................................................................................................... 367

CHAPTER 12 Organometallic Compounds of the Main Group Elements ..............................375

12.1 Preparation of Organometallic Compounds ........................................................... 376
12.2 Organometallic Compounds of Group IA Metals................................................... 378
12.3 Organometallic Compounds of Group IIA Metals.................................................. 380
12.4 Organometallic Compounds of Group IIIA Metals ................................................ 383
12.5 Organometallic Compounds of Group IVA Metals ................................................ 387
12.6 Organometallic Compounds of Group VA Elements ............................................. 388
12.7 Organometallic Compounds of Zn, Cd, and Hg ..................................................... 389

CHAPTER 13 Chemistry of Nonmetallic Elements I. Hydrogen, Boron, Oxygen, and

Carbon ....................................................................................................................393
13.1 Hydrogen .................................................................................................................... 393
13.2 Boron ........................................................................................................................... 400
13.3 Oxygen ........................................................................................................................ 411
13.4 Carbon......................................................................................................................... 420

CHAPTER 14 Chemistry of Nonmetallic Elements II. Groups IVA and VA ...........................439

14.1 The Group IVA Elements.......................................................................................... 439
14.2 Nitrogen ...................................................................................................................... 456
14.3 Phosphorus, Arsenic, Antimony, and Bismuth ...................................................... 471

CHAPTER 15 Chemistry of Nonmetallic Elements III. Groups VIAeVIIIA ............................499

15.1 Sulfur, Selenium, and Tellurium ............................................................................... 499
15.2 The Halogens ............................................................................................................. 520
15.3 The Noble Gases........................................................................................................ 538

PART 5 Chemistry of Coordination Compounds .......................................... 551

CHAPTER 16 Introduction to Coordination Chemistry ............................................................553
16.1 Structures of Coordination Compounds................................................................ 553
16.2 MetaleLigand Bonds............................................................................................... 557
16.3 Naming Coordination Compounds ........................................................................ 559
16.4 Isomerism ................................................................................................................. 561
16.5 A Simple Valence Bond Description of Coordinate Bonds ................................. 568
 Contents ix

16.6 Magnetism................................................................................................................ 572

16.7 A Survey of Complexes of First-Row Metals........................................................ 574
16.8 Complexes of Second- and Third-Row Metals ..................................................... 576
16.9 The 18-Electron Rule ............................................................................................... 576
16.10 Back Donation .......................................................................................................... 580
16.11 Complexes of Dinitrogen, Dioxygen, and Dihydrogen ........................................ 585

CHAPTER 17 Ligand Fields and Molecular Orbitals ................................................................591

17.1 Splitting of d Orbital Energies in Octahedral Fields ............................................. 591
17.2 Splitting of d Orbital Energies in Fields of Other Symmetry................................ 594
17.3 Factors Affecting D .................................................................................................... 598
17.4 Consequences of Crystal Field Splitting ................................................................. 600
17.5 JahneTeller Distortion .............................................................................................. 603
17.6 Spectral Bands ........................................................................................................... 604
17.7 Molecular Orbitals in Complexes............................................................................. 606

CHAPTER 18 Interpretation of Spectra ......................................................................................617

18.1 Splitting of Spectroscopic States.............................................................................. 617
18.2 Orgel Diagrams .......................................................................................................... 621
18.3 Racah Parameters and Quantitative Methods ....................................................... 624
18.4 The Nephelauxetic Effect ......................................................................................... 627
18.5 TanabeeSugano Diagrams ....................................................................................... 629
18.6 The Lever Method ..................................................................................................... 633
18.7 Jørgensen’s Method .................................................................................................. 636
18.8 Charge Transfer Absorption..................................................................................... 637
18.9 Solvatochromism........................................................................................................ 639

CHAPTER 19 Composition and Stability of Complexes ...........................................................643

19.1 Composition of Complexes in Solution ................................................................... 643
19.2 Job’s Method of Continuous Variations .................................................................. 645
19.3 Equilibria Involving Complexes ............................................................................... 647
19.4 Distribution Diagrams ............................................................................................... 652
19.5 Factors Affecting the Stability of Complexes......................................................... 655

CHAPTER 20 Synthesis and Reactions of Coordination Compounds ....................................665

20.1 Synthesis of Coordination Compounds................................................................. 665
20.2 Substitution Reactions in Octahedral Complexes ............................................... 671
20.3 Ligand Field Effects................................................................................................. 678
20.4 Acid-Catalyzed Reactions of Complexes .............................................................. 681
20.5 Base-Catalyzed Reactions of Complexes.............................................................. 682
20.6 The Compensation Effect ....................................................................................... 684
20.7 Linkage Isomerization............................................................................................. 685
x Contents

20.8 Substitution in Square Planar Complexes ............................................................ 687

20.9 The Trans Effect ...................................................................................................... 690
20.10 Electron Transfer Reactions ................................................................................... 694
20.11 Reactions in Solid Coordination Compounds ....................................................... 697

CHAPTER 21 Complexes Containing MetaleCarbon and MetaleMetal Bonds....................707

21.1 Binary Metal Carbonyls .......................................................................................... 707
21.2 Structures of Metal Carbonyls................................................................................ 711
21.3 Bonding of Carbon Monoxide to Metals ............................................................... 712
21.4 Preparation of Metal Carbonyls ............................................................................. 715
21.5 Reactions of Metal Carbonyls ................................................................................ 716
21.6 Structure and Bonding in MetaleAlkene Complexes ......................................... 721
21.7 Preparation of MetaleAlkene Complexes............................................................. 727
21.8 Chemistry of Cyclopentadienyl and Related Complexes.................................... 728
21.9 Bonding in Ferrocene .............................................................................................. 732
21.10 Reactions of Ferrocene and other Metallocenes.................................................. 735
21.11 Complexes of Benzene and Related Aromatics ................................................... 738
21.12 Compounds Containing MetaleMetal Bonds....................................................... 741

CHAPTER 22 Coordination Compounds in Catalysis...............................................................747

22.1 Elementary Steps in Catalytic Processes................................................................ 748
22.2 Homogeneous Catalysis ........................................................................................... 761

CHAPTER 23 Bioinorganic Chemistry........................................................................................773

23.1 What Metals Do in Some Living Systems ............................................................... 773
23.2 Cytotoxicity of Some Metal Compounds................................................................. 784
23.3 Antimalarial Metallodrugs ........................................................................................ 792

APPENDIX A: Ionization Energies..............................................................................................797

APPENDIX B: Character Tables for Selected Point Groups.....................................................801
INDEX.............................................................................................................................................807
Preface to the Second Edition

The development of inorganic continues at an astonishing pace, and the number of journal pages
devoted annually to the field continues to increase. Since the publication of the first edition of this
book, exciting results have been obtained in many areas, especially in the application of inorganic
compounds in medicine.
The present edition continues the same format as the first with five major areas that constitute atomic
and molecular structure; condensed phases; acids, bases, and solvents; chemistry of the elements; and
chemistry of coordination compounds. Although the structure of the book has not been changed, there
are some significant modifications. First, the coverage of superacids in Chapter 10 has been expanded in
order to reflect the increasing utilization of these materials in inorganic chemistry. Second, a new
chapter on bioinorganic chemistry has been added, with numerous illustrations from the recent liter-
ature that describe the use of metal complexes in medicine. Third, the coverage of catalysis by complexes
has been expanded with new material on mechanisms. Fourth, the entire manuscript has been edited to
enhance clarity of presentation. The judicious use of color illustrations is also new to this edition.
Finally, a significant number of additional end of chapter questions and problems have been added.
Although there have been substantial changes in the coverage from the first edition, flexibility in the
order of presentation remains. After the introductory chapters on atomic and molecular structure, the
nature of inorganic condensed phases is described with a theme of understanding properties of such
materials. Chapter 8 deals with dynamic processes in solids because of the importance of the topic in
many industrial processes.
Explanations do not exist for all observations in the behavior of inorganic compounds. Conse-
quently, throughout the text there are instances mentioned which illustrate unanswered questions in
science. It is hoped that some of these might generate an interest that would cause the reader to pursue
further study in inorganic chemistry.
The author wishes to thank all of those students who have used the first edition and pointed out
errors. Their contribution to the preparation of the second edition is gratefully acknowledged. The
author also wishes to thank his wife, Kathleen, for enduring yet another long project.

xi
Preface to the First Edition

No single volume, certainly not a textbook, can come close to including all of the important topics in
inorganic chemistry. The field is simply too broad in scope and it is growing at a rapid pace. Inorganic
chemistry textbooks reflect a great deal of work and the results of the many choices that authors must
make as to what to include and what to leave out. Writers of textbooks in chemistry bring to the task
backgrounds that reflect their research interests, the schools they attended, and their personalities. In
their writing, authors are really saying “this is the field as I see it.” In these regards, this book is similar to
others.
When teaching a course in inorganic chemistry, certain core topics are almost universally included. In
addition, there are numerous peripheral areas that may be included at certain schools but not at others
depending on the interests and specialization of the person teaching the course. The course content may
even change from one semester to the next. The effort to produce a textbook that presents coverage of
a wide range of optional material in addition to the essential topics can result in a textbook for a one
semester course that contains a thousand pages. Even a “concise” inorganic chemistry book can be
nearly this long. This book is not a survey of the literature or a research monograph. It is a textbook that
is intended to provide the background necessary for the reader to move on to those more advanced
resources.
In writing this book, I have attempted to produce a concise textbook that meets several objectives.
First, the topics included were selected in order to provide essential information in the major areas of
inorganic chemistry (molecular structure, acidebase chemistry, coordination chemistry, ligand field
theory, solid-state chemistry, etc.). These topics form the basis for competency in inorganic chemistry at
a level commensurate with the one semester course taught at most colleges and universities.
When painting a wall, better coverage is assured when the roller passes over the same area several
times from different directions. It is the opinion of the author that this technique works well in
teaching chemistry. Therefore, a second objective has been to stress fundamental principles in the
discussion of several topics. For example, the hardesoft interaction principle is employed in
discussion of acidebase chemistry, stability of complexes, solubility, and predicting reaction prod-
ucts. Third, the presentation of topics is made with an effort to be clear and concise so that the book
is portable and user friendly. This book is meant to present in convenient form a readable account of
the essentials of inorganic chemistry that can serve as both as a textbook for a one semester course,
upper-level course and as a guide for self study. It is a textbook not a review of the literature or
a research monograph. There are few references to the original literature, but many of the advanced
books and monographs are cited. xii
 Preface to the First Edition xiii

Although the material contained in this book is arranged in a progressive way, there is flexibility in
the order of presentation. For students, who have a good grasp of the basic principles of quantum
mechanics and atomic structure, Chapters 1 and 2 can be given a cursory reading but not included in
the required course material. The chapters are included to provide a resource for review and self study.
Chapter 4 presents an overview of structural chemistry early so the reader can become familiar with
many types of inorganic structures before taking up the study of symmetry or chemistry of specific
elements. Structures of inorganic solids are discussed in Chapter 7, but that material could easily be
studied before Chapters 5 or 6. Chapter 6 contains material dealing with intermolecular forces and
polarity of molecules because of the importance of these topics when interpreting properties of
substances and their chemical behavior. In view of the importance of the topic, especially in industrial
chemistry, this book includes material on rate processes involving inorganic compounds in the solid
state (Chapter 8). The chapter begins with an overview of some of the important aspects of reactions in
solids before considering phase transitions and reactions of solid coordination compounds.
It should be an acknowledged fact that no single volume can present the descriptive chemistry of all
the elements. Some of the volumes that attempt to do so are enormous. In this book, the presentation
of descriptive chemistry of the elements is kept brief with the emphasis placed on types of reactions and
structures that summarize the behavior of many compounds. The attempt is to present an overview of
descriptive chemistry that will show the important classes of compounds and their reactions without
becoming laborious in its detail. Many schools offer a descriptive inorganic chemistry course at an
intermediate level that covers a great deal of the chemistry of the elements. Part of the rationale for
offering such a course is that the upper-level course typically concentrates more heavily on principles of
inorganic chemistry. Recognizing that an increasing fraction of the students in the upper-level inorganic
chemistry course will have already had a course that deals primarily with descriptive chemistry, this
book is devoted to a presentation of the principles of inorganic chemistry while giving a brief overview
of descriptive chemistry in Chapters 12e15, although many topics that are primarily descriptive in
nature are included in other sections. Chapter 16 provides a survey of the chemistry of coordination
compounds and that is followed by Chapters 17e23 that deal with structures, bonding, spectra, and
reactions of coordination compounds. The material included in this text should provide the basis for
the successful study of a variety of special topics.
Doubtless, the teacher of inorganic chemistry will include some topics and examples of current or
personal interest that are not included in any textbook. That has always been my practice, and it
provides an opportunity to show how the field is developing and new relationships.
Most textbooks are an outgrowth of the author’s teaching. In the preface, the author should convey
to the reader some of the underlying pedagogical philosophy which resulted in the design of his or her
book. It is unavoidable that a different teacher will have somewhat different philosophy and meth-
odology. As a result, no single book will be completely congruent with the practices and motivations of
all teachers. A teacher who writes the textbook for his or her course should find all of the needed topics
in the book. However, it is unlikely that a book written by someone else will ever contain exactly the
right topics presented in exactly the right way.
The author has taught several hundred students in inorganic chemistry courses at Illinois State
University, Illinois Wesleyan University, University of Illinois, and Western Kentucky University using
the materials and approaches set forth in this book. Among that number are many who have gone onto
graduate school, and virtually all of that group have performed well (in many cases very well!) on
xiv Preface to the First Edition

registration and entrance examinations in inorganic chemistry at some of the most prestigious insti-
tutions. Although it is not possible to name all of those students, they have provided the inspiration to
see this project to completion with the hope that students at other universities may find this book useful
in their study of inorganic chemistry. It is a pleasure to acknowledge and give thanks to Derek Coleman
for his encouragement and consideration as this project progressed. Finally, I would like to thank my
wife, Kathleen, for reading most of the manuscript and making many helpful suggestions. Her constant
encouragement and support have been needed at many times as this project was underway.