Principles of Inorganic Chemistry: Basics and Applications

Preface
Acknowledgements
Contents
1 Atoms and Electrons
	Abstract
	1.1 Introduction
	1.2 The Bohr Atom
	1.3 Electron as a Wave
	1.4 The Schrödinger Equation
		1.4.1 Schrödinger Equation Solution for One-Electron Systems
	1.5 Quantum Numbers
	1.6 Orbital Representations
		1.6.1 Two-Dimensional Representations
		1.6.2 Three-Dimensional Representations
	1.7 Multi-Electron Atoms
		1.7.1 Putting Electrons into Atomic Orbitals
		1.7.2 Exceptions to Madelung’s Rule
2 The Periodic Table
	Abstract
	2.1 Early Development
	2.2 Structure of the Periodic Table
	2.3 Periodic Trends of Some Physical Properties of Atoms
		2.3.1 Ionization Energy
		2.3.2 Electron Affinity
		2.3.3 Electronegativity
		2.3.4 Covalent, Ionic, or Metallic Bonding, and Electronegativity
		2.3.5 Atom Size
		2.3.6 Bond Valence Model
		2.3.7 Ionic Radii
		2.3.8 Periodic Trends in Atom Sizes
	2.4 Summary of Periodic Trends
	2.5 Supporting Information
3 Covalent Bonding Theories
	Abstract
	3.1 Introduction
	3.2 Lewis Electron Dot Theory
		3.2.2 Expanded Octet
		3.2.4 Problems for the Octet Rule
	3.3 Valence Shell Electron Pair Repulsion, VSEPR, Theory
		3.3.1 Geometrical Arrangements from VSEPR Theory
		3.3.2 Structural Trends and VSEPR Theory
		3.3.3 Problems with VSEPR Theory
	3.4 Valence Bond Theory
		3.4.1 Hybridization of Orbitals
		3.4.2 Multiple Bonds and Resonance
		3.4.3 Hybridization of d Orbitals
		3.4.4 Summary of Problems and Advances
	3.5 Molecular Orbital Theory
		3.5.1 Basics of the Theory
		3.5.2 Molecular Orbitals from p Valence Orbitals in Diatomic Species
		3.5.3 Molecular Orbital Electronic Configurations of Diatomic Species
		3.5.4 Photoelectron Spectroscopy
		3.5.5 Photoelectron Spectra of O2 and N2
		3.5.6 Orbital Mixing in Molecular Orbital Theory
		3.5.7 Molecular Orbitals in Heteronuclear Diatomic Species
		3.5.8 Molecular Orbitals in Triatomic Species
		3.5.9 Molecular Orbitals for Linear and Bent Triatomic Species
		3.5.10 Trihalide Anions and Related Hypervalent Species
		3.5.11 Methane
	3.6 Putting It All Together
	3.7 Supporting Information
		3.7.1 Secular Equation Solution for a Homonuclear Triatomic System
4 Energy
	Abstract
	4.1 Introduction
		4.1.1 Basic Thermodynamic Relationships
		4.1.2 Gibbs Free Energy and the Equilibrium Constant
	4.2 Bond Energies and Bond Dissociation Enthalpies
		4.2.1 Average Bond Dissociation Enthalpies
		4.2.2 Applications of Bond Dissociation Enthalpies
	4.3 Thermodynamics and Chemical Cycles
		4.3.1 Process Chemical Cycles
		4.3.2 Isothermal Chemical Cycles
		4.3.3 Lattice Energies and Interionic Distances
		4.3.4 Lattice Energies and Molecular Volumes
		4.3.5 Other Isothermal Cycles
5 Acids and Bases
	Abstract
	5.1 Introduction
	5.2 Brønsted or Protic Acids and Bases
		5.2.1 Characteristics of Brønsted Acids and Bases
		5.2.2 Strengths of Brønsted Acids and Bases
		5.2.3 Strengths of Strong Brønsted Acids
		5.2.4 Brønsted Superacids
		5.2.5 Brønsted Superbases
	5.3 Lewis Acids and Bases
		5.3.1 Strengths of Lewis Acids and Bases
		5.3.2 Single Reference Scales of Acidity and Basicity
		5.3.3 The Dual Parameter E and C Model for Lewis Acidity and Basicity
		5.3.4 Some General Trends in Lewis Acidities
		5.3.5 The Hard and Soft Model for Lewis Acidity and Basicity
		5.3.6 Frustrated Lewis Pairs, FLPs
6 Reaction Types and Mechanisms
	Abstract
	6.1 Introduction
	6.2 Reaction Types
		6.2.1 Proton-Transfer Reactions
		6.2.2 Substitution Reactions
		6.2.3 Oxidation–Reduction Reactions
		6.2.4 Oxidative-Addition Reactions
	6.3 Kinetic Background
		6.3.1 The Rate Law
		6.3.2 Temperature and Pressure Effects
		6.3.3 Ionic Strength Effects
	6.4 Proton-Transfer Mechanisms
	6.6 Oxidation–Reduction Reaction Mechanisms
		6.6.1 Reaction Types
		6.6.2 Inner-Sphere Electron Transfer
		6.6.3 Outer-Sphere Electron Transfer
	6.7 Oxidative-Addition Reaction Mechanisms
		6.7.1 Oxidative Addition of X–Y Molecules
		6.7.2 Oxidative Addition of Organic Halides to Transition Metals
	6.8 Isomerization Reaction Mechanisms
		6.8.1 Linkage Isomerization
		6.8.2 Geometrical Isomerization
	6.9 Supporting Information
		6.9.1 Rate Laws
		6.9.2 Rapid-Equilibrium Assumption
		6.9.3 Steady-State Assumption
7 The Solid State and Symmetry
	Abstract
	7.1 Introduction
	7.2 Some Elements of Group Theory
		7.2.1 Symmetry Operations and Point Groups
		7.2.2 Group Theory and Vibrational Spectroscopy
		7.2.3 Selection Rules in Vibrational Spectroscopy
		7.2.4 Group Theory and Orbitals
	7.3 Crystalline Inorganic Solids
		7.3.1 Introduction
		7.3.2 Some Common Structure Types
		7.3.3 Radius-Ratio Method
		7.3.4 Polymorphs and Polytypes
	7.4 Metals
		7.4.1 Properties of Metals
		7.4.2 Structures of Metals
		7.4.3 Bonding in Metals
	7.5 Electrical Insulators and Semiconductors
	7.6 Spinels and Perovskites
		7.6.1 Structures of Spinels
		7.6.2 Structures of Perovskites
	7.7 Supporting Information
		7.7.1 Crystal Structures: Seeing the Picture
		7.7.2 Ionic Radii
8 Introduction to Transition Metals
	Abstract
	8.1 Introduction
	8.2 Coordination Compounds
	8.3 Ligand Types in Coordination Compounds
	8.4 Ligand Arrangements and Isomers
		8.4.1 Octahedral, Square Planar, and Tetrahedral Systems
		8.4.2 Other Ligand Arrangements
		8.4.3 Ionization Isomers
		8.4.4 Hydrate Isomers
		8.4.5 Optical Isomers
		8.4.6 Meso Isomers
		8.4.8 Conformational Isomers
		8.4.9 Isomers as Templates for Open-Framework Materials
	8.5 Bonding Theories for Transition-Metal Complexes
		8.5.1 Historical Background
		8.5.2 Crystal Field Theory
		8.5.4 Ligand Field Theory
	8.6 Electronic Spectra: Colors
		8.6.1 Electronic States and Term Symbols
		8.6.2 Electronic States in an Octahedral Field
		8.6.3 Energy Units in Electronic Spectroscopy
		8.6.4 Energies of Russell–Saunders Terms and Ligand Field States
		8.6.5 Electronic Spectra of d3 and d8 Systems
		8.6.6 Electronic Spectra of d6 Systems
	8.7 Trends in Values of ∆ and B
	8.8 Six-Coordinate Complexes of Lower Symmetry than Oh
	8.9 Magnetic Properties
		8.9.1 Basic Concepts and Terminology
		8.9.2 Magnetic Moment and Unpaired Electrons
		8.9.3 Representative Examples of Magnetic Behavior
9 The Transition Metals: Groups 3–12
	Abstract
	9.2 General Properties of the Transition Metals
	9.3 Group 3: Scandium, Yttrium, and Lanthanum
	9.4 Group 4: Titanium, Zirconium, and Hafnium
	9.5 Group 5: Vanadium, Niobium, and Tantalum
	9.6 Group 6: Chromium, Molybdenum, and Tungsten
	9.7 Group 7: Manganese, Technetium, and Rhenium
	9.8 Group 8: Iron, Ruthenium, and Osmium
	9.9 Group 9: Cobalt, Rhodium, and Iridium
	9.10 Group 10: Nickel, Palladium, and Platinum
	9.11 Group 11: Copper, Silver, and Gold
	9.12 Group 12: Zinc, Cadmium, and Mercury
10 Organometallic Chemistry of Transition Metals
	Abstract
	10.1 What Is Organometallic?
	10.2 Bonding in Organometallic Systems
		10.2.2 Arrangement of Organometallic Substituents
		10.2.3 Bonding in Metal Carbonyls
		10.2.4 Bonding in Metal Bis-Cyclopentadiene Species
11 The Lanthanides
	Abstract
	11.1 Introduction
	11.2 Extraction and Separation of the Lanthanides
	11.3 The Elements
	11.4 The Lanthanide Contraction
	11.5 Compounds of the Lanthanides
		11.5.1 Oxides of the Lanthanides
		11.5.2 Halides of the Lanthanides
		11.5.3 Organometallic Lanthanides
12 Groups 1 and 2
	Abstract
	12.1 Introduction: The Elements
	12.2 Natural Sources and Preparation of the Elements
		12.2.2 Lithium
		12.2.3 Sodium
		12.2.4 Potassium, Rubidium, and Cesium
		12.2.6 Magnesium
		12.2.7 Calcium
		12.2.8 Strontium and Barium
	12.3 Structures, Properties, and Uses of the Elements
		12.3.1 Hydrogen
		12.3.2 The Alkali Metals
		12.3.3 The Alkaline Earth Metals
	12.4 Binary Compounds with Oxygen
		12.4.1 The Oxide and Peroxide of Hydrogen
		12.4.2 Oxides of the Alkali Metals
		12.4.3 Oxides of the Alkaline Earth Metals
		12.4.4 Peroxides of the Alkali and Alkaline Earth Metals
		12.4.5 Superoxides of the Alkali Metals
		12.4.6 Ozonides of the Alkali Metals
	12.5 Aqueous Ions
		12.5.1 The Hydrated Proton
		12.5.2 Aqueous Cations
		12.5.3 Aqueous Anions
	12.6 Binary Carbides of the Metals of Groups 1 and 2
	12.7 Binary Nitrides of the Metals of Groups 1 and 2
13 Group 13
	Abstract
	13.1 Introduction: The Elements
	13.2 Natural Sources and Preparation of the Elements
		13.2.1 Boron
		13.2.2 Aluminum
		13.2.3 Gallium, Indium, and Thallium
	13.3 Structures, Properties, and Uses of the Elements
		13.3.1 Boron
		13.3.2 Aluminum
		13.3.3 Gallium, Indium, and Thallium
	13.4 Oxides
		13.4.1 General Features
		13.4.2 Boron Oxides
		13.4.3 Aluminum Oxides
		13.4.4 Gallium and Indium Oxides
		13.4.5 Thallium Oxides
	13.5 Borates, Boric Acid, and Their Derivatives
		13.5.1 Borate Anion Structures
		13.5.2 Boric Acid and Metaboric Acid Structures
		13.5.3 Boric Acid and Its Esters in Aqueous Solution
		13.5.4 Boronic Acids
	13.6 Aluminum, Gallium, and Indium Hydroxides and Aqua Ions
		13.6.1 Aluminum Hydroxide
		13.6.2 Aqueous Al(III)
		13.6.3 Gallium and Indium Hydroxides and Aqua Ions
	13.7 Borides
	13.8 Nitrides
		13.8.1 Boron Nitride
		13.8.2 Aluminum Nitride
		13.8.3 Gallium Nitride
		13.8.4 Indium Nitride
	13.9 Carbides
		13.9.1 Boron Carbide
		13.9.2 Aluminum Carbide
	13.10 Hydrides
		13.10.1 Tetrahydride Anions of Boron and Aluminum
		13.10.2 Boron Hydrides
		13.10.3 Boron Hydride Derivatives
		13.10.4 Carboranes
		13.10.5 Metallacarboranes
		13.10.6 Aluminum Hydride
	13.11 Halides
		13.11.1 Properties and Structures
		13.11.2 Trihalides as Lewis Acids
	13.12 Organic Derivatives
		13.12.1 Properties and Structures
		13.12.2 Activators for Olefin Polymerization
		13.12.3 Fluorinated Organoboron Derivatives
		13.12.4 Organoboron Derivatives in Hydroboration and C–C Bond Formation
14 Group 14
	Abstract
	14.1 Introduction: The Elements
	14.2 Natural Sources and Preparation of the Elements
		14.2.1 Carbon
		14.2.2 Silicon
		14.2.3 Germanium
		14.2.4 Tin
		14.2.5 Lead
	14.3 Structures, Properties, and Uses of the Elements
		14.3.1 Common Allotropes of Carbon
		14.3.2 Fullerenes
		14.3.3 Carbon Nanotubes
		14.3.4 Graphene
		14.3.5 Silicon
		14.3.6 Germanium
		14.3.7 Tin
		14.3.8 Lead
	14.4 Oxides
		14.4.1 The Gaseous Monoxides
		14.4.2 The Solid Monoxides
		14.4.3 Carbon Dioxide, CO2
		14.4.4 Silicon Dioxide or Silica, SiO2
		14.4.5 Germanium Dioxide, GeO2
		14.4.6 The Oxides of Tin(IV) and Lead(IV)
	14.5 Oxoacids, Oxanions, and Aqueous Cations
		14.5.1 Carbon Oxoacids and Oxoanions
		14.5.2 Silicon Oxoacids and Oxoanions
		14.5.3 Germanium Oxoacids and Oxoanions
		14.5.4 Tin and Lead Aqua Cations and Oxoanions
	14.6 Halides
		14.6.1 The Tetrahalides
		14.6.2 The Dihalides
		14.6.3 Lewis Base Adducts of Group 14 Halides
	14.7 Organic Derivatives of Si, Ge, Sn, and Pb
	14.8 Silicones
	14.9 Catenation
		14.9.1 Catenation with Single Bonds
		14.9.2 Catenation with Double Bonds
		14.9.3 Catenation with Triple Bonds
	14.10 Amines and Nitrides
		14.10.1 Amines
		14.10.2 Nitrides
15 Group 15
	Abstract
	15.1 Introduction: The Elements
	15.2 Natural Sources and Preparation of the Elements
		15.2.1 Nitrogen
		15.2.2 Phosphorus
		15.2.3 Arsenic, Antimony, and Bismuth
	15.3 Structures, Properties, and Uses of the Elements
		15.3.1 Dinitrogen or Nitrogen
		15.3.2 Phosphorus
		15.3.3 Arsenic, Antimony, and Bismuth
	15.4 Oxides
		15.4.1 Oxides of Nitrogen
		15.4.2 Oxides of Phosphorus
		15.4.3 Oxides of Arsenic, Antimony, and Bismuth
	15.5 Oxoacids and Oxoanions
	15.6 Hydrides
		15.6.1 The AH3 Hydrides: Properties and Structures
		15.6.2 Ammonia
		15.6.3 Hydrazine
		15.6.4 Diazene
		15.6.5 Hydroxylamine
		15.6.7 Hydrides of Phosphorus, Arsenic, Antimony, and Bismuth
	15.7 Halides
		15.7.1 The Trihalides, AX3
		15.7.2 The Pentahalides, AX5
		15.7.3 The Oxohalides, OAX3
		15.7.4 Mixed Halides of Phosphorus: Halogen Exchange
		15.7.5 Phosphorus(III) Halide Derivatives: Phosphenium Ions
	15.8 Binary Nitrides
		15.8.1 Classification of Nitrides
		15.8.2 Preparations and Uses of Some Nitrides
		15.8.3 Structures of Representative Nitrides
	15.9 Organic Amines, Phosphanes, and Related Compounds
		15.9.1 Organic Derivatives of the AL3 Type
		15.9.2 Organic Derivatives of the AL5 Type
		15.9.3 Preparations and Uses of Some Organic Amines and Phosphanes
		15.9.4 Phosphanes as Ligands in Organometallic Chemistry
16 Group 16
	Abstract
	16.1 Introduction: The Elements
	16.2 Natural Sources and Preparation of the Elements
		16.2.1 Oxygen
		16.2.2 Sulfur
		16.2.3 Selenium and Tellurium
	16.3 Structures, Properties, and Uses of the Elements
		16.3.1 Dioxygen or Oxygen
		16.3.2 Singlet Oxygen
		16.3.3 Ozone and Covalent Ozonides
		16.3.4 Sulfur
		16.3.5 Selenium, Tellurium, and Polonium
	16.4 Oxides, Oxoacids, and Oxoanions
		16.4.1 Oxoanions of Oxygen
		16.4.2 Oxides, Oxoacids, and Oxoanions of Sulfur
		16.4.3 Oxides, Oxoacids, and Oxoanions of Selenium and Tellurium
	16.6 Hydrides
	16.7 Nitrides of Sulfur
	16.8 Organic Derivatives
17 Group 17
	Abstract
	17.1 Introduction: The Elements
	17.2 Natural Sources and Preparation of the Elements
		17.2.1 Fluorine
		17.2.2 Chlorine
		17.2.3 Bromine
		17.2.4 Iodine
	17.3 Structures, Properties, and Uses of the Elements
	17.4 Oxides, Oxoacids, and Oxoanions
		17.4.1 Oxygen Halides, Hypohalous Acids, and Hypohalites
		17.4.2 The Halogen Dioxides
		17.4.3 The Halites and Halous Acids
		17.4.4 The Halates and Halic Acids
		17.4.5 The Perhalates and Perhalic Acids
	17.5 Polyhalogens and Polyinterhalogens
		17.5.1 Properties of Some Polyhalogens and Polyinterhalogens
18 Group 18
	Abstract
	18.1 Introduction: The Elements
	18.2 Natural Sources and Preparation of the Elements
		18.2.1 Helium
		18.2.2 Neon, Argon, Kryton, and Xenon
	18.3 Structures, Properties, and Uses of the Elements
		18.3.1 Helium
		18.3.2 Neon, Argon, Krypton, and Xenon
	18.4 Chemical Derivatives of the Noble Gases
		18.4.1 Binary Fluorides of Xenon and Krypton
		18.4.2 Binary Oxides and Oxoanions of Xenon
		18.4.3 Oxofluorides of Xenon
		18.4.4 Species Formed by Argon
19 Bioinorganic Chemistry
	Abstract
	19.1 Introduction
	19.2 Functions of Some Main Group Elements
		19.2.1 Iodine and Selenium
	19.3 Functions of Some Transition Metals
		19.3.1 Zinc in Human Carbonic Anhydrase, hCA II
		19.3.2 Zinc in Peptidases
		19.3.3 Cobalt in Coenzyme B12
		19.3.4 Cobalt in a Mutase and a Synthase
		19.3.5 Iron in Porphyrins and Hemoglobin
		19.3.6 Iron in Cytochrome P450s
20 Nanomaterials
	Abstract
	20.1 Introduction
	20.2 Formation of Nanomaterials
		20.2.1 Rate of Growth
		20.2.2 Surface Energy and Growth
		20.2.3 Determination of the Sizes of Nanoparticles
		20.2.4 Colors of Nanoparticles
	20.3 Synthesis and Properties of Some Nanomaterials
		20.3.1 Synthesis of Gold Nanoparticles, Au NPs
		20.3.2 Synthesis of Silver Nanoparticles, Ag NPs
		20.3.3 Synthesis of Copper Nanoparticles, Cu NPs
		20.3.4 Synthesis of Iron Nanoparticles, Fe NPs
		20.3.5 Synthesis of Palladium and Platinum Nanoparticles, Pd NPs and Pt NPs
		20.3.6 Synthesis of Silicon Nanoparticles, Si NPs
		20.3.7 Synthesis of Metal-Oxide Nanoparticles
		20.3.8 Synthesis of Binary Semiconductor Nanoparticles
	20.4 Biological Uses and Effects of Nanomaterials
Index