Inorganic chemistry

Cover
Preface
About the authors
Acknowledgements
About the book
Online resources
Summary of contents
Detailed contents
Glossary of chemical abbreviations
Part 1 Foundations
	1 Atomic structure
		The structures of hydrogenic atoms
			1.1 Spectroscopic information
			1.2 Some principles of quantum mechanics
			1.3 Atomic orbitals
		Many-electron atoms
			1.4 Penetration and shielding
			1.5 The building-up principle
			1.6 The classification of the elements
			1.7 Atomic properties
		FURTHER READING
		EXERCISES
		TUTORIAL PROBLEMS
	2 Molecular structure and bonding
		Lewis structures
			2.1 The octet rule
			2.2 Resonance
			2.3 The VSEPR model
		Valence bond theory
			2.4 The hydrogen molecule
			2.5 Homonuclear diatomic molecules
			2.6 Polyatomic molecules
		Molecular orbital theory
			2.7 An introduction to the theory
			2.8 Homonuclear diatomic molecules
			2.9 Heteronuclear diatomic molecules
			2.10 Bond properties
		Bond properties, reaction enthalpies, and kinetics
			2.11 Bond length
			2.12 Bond strength and reaction enthalpies
			2.13 Electronegativity and bond enthalpy
			2.14 An introduction to catalysis
		FURTHER READING
		EXERCISES
		TUTORIAL PROBLEMS
	3 Molecular symmetry
		An introduction to symmetry analysis
			3.1 Symmetry operations, elements, andpoint groups
			3.2 Character tables
		Applications of symmetry
			3.3 Polar molecules
			3.4 Chiral molecules
			3.5 Molecular vibrations
		The symmetries of molecular orbitals
			3.6 Symmetry-adapted linear combinations
			3.7 The construction of molecular orbitals
			3.8 The vibrational analogy
		Representations
			3.9 The reduction of a representation
			3.10 Projection operators
			3.11 Polyatomic molecules
		FURTHER READING
		EXERCISES
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	4 The structures of simple solids
		The description of the structures of solids
			4.1 Unit cells and the descriptionof crystal structures
			4.2 The close packing of spheres
			4.3 Holes in close-packed structures
		The structures of metals and alloys
			4.4 Polytypism
			4.5 Nonclose-packed structures
			4.6 Polymorphism of metals
			4.7 Atomic radii of metals
			4.8 Alloys and interstitials
		Ionic solids
			4.9 Characteristic structures of ionic solids
			4.10 The rationalization of structures
		The energetics of ionic bonding
			4.11 Lattice enthalpy and theBorn–Haber cycle
			4.12 The calculation of lattice enthalpies
			4.13 Comparison of experimental and theoretical values
			4.14 The Kapustinskii equation
			4.15 Consequences of lattice enthalpies
		Defects and nonstoichiometry
			4.16 The origins and types of defects
			4.17 Nonstoichiometric compounds and solid solutions
		The electronic structures of solids
			4.18 The conductivities of inorganic solids
			4.19 Bands formed from overlapping atomic orbitals
			4.20 Semiconduction
		Further information: the Born–Mayer equation
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		EXERCISES
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	5 Acids and bases
		Brønsted acidity
			5.1 Proton transfer equilibria in water
		Characteristics of Brønsted acids
			5.2 Periodic trends in aqua acid strength
			5.3 Simple oxoacids
			5.4 Anhydrous oxides
			5.5 Polyoxo compound formation
		Lewis acidity
			5.6 Examples of Lewis acids and bases
			5.7 Group characteristics of Lewis acids
			5.8 Hydrogen bonding
		Reactions and properties of Lewis acids and bases
			5.9 The fundamental types of reaction
			5.10 Factors governing interactions between Lewis acids and bases
			5.11 Thermodynamic Lewis acidity parameters
		Nonaqueous solvents
			5.12 Solvent levelling
			5.13 The Hammett acidity function and its application to strong, concentrated acids
			5.14 The solvent system definition of acids and bases
			5.15 Solvents as acids and bases
		Applications of acid–base chemistry
			5.16 Superacids and superbases
			5.17 Heterogeneous acid–base reactions
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	6 Oxidation and reduction
		Reduction potentials
			6.1 Redox half-reactions
			6.2 Standard potentials and spontaneity
			6.3 Trends in standard potentials
			6.4 The electrochemical series
			6.5 The Nernst equation
		Redox stability
			6.6 The influence of pH
			6.7 Reactions with water
			6.8 Oxidation by atmospheric oxygen
			6.9 Disproportionation and comproportionation
			6.10 The influence of complexation
			6.11 The relation between solubility and standard potentials
		Diagrammatic presentation of potential data
			6.12 Latimer diagrams
			6.13 Frost diagrams
			6.14 Proton-coupled electron transfer: Pourbaix diagrams
			6.15 Applications in environmental chemistry: natural waters
		Chemical extraction of the elements
			6.16 Chemical reduction
			6.17 Chemical oxidation
			6.18 Electrochemical extraction
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	7 An introduction to coordination compounds
		The language of coordination chemistry
			7.1 Representative ligands
			7.2 Nomenclature
		Constitution and geometry
			7.3 Low coordination numbers
			7.4 Intermediate coordination numbers
			7.5 Higher coordination numbers
			7.6 Polymetallic complexes
		Isomerism and chirality
			7.7 Square-planar complexes
			7.8 Tetrahedral complexes
			7.9 Trigonal-bipyramidal and square-pyramidalcomplexes
			7.10 Octahedral complexes
			7.11 Ligand chirality
		The thermodynamics of complex formation
			7.12 Formation constants
			7.13 Trends in successive formation constants
			7.14 The chelate and macrocyclic effects
			7.15 Steric effects and electron delocalization
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	8 Physical techniques in inorganic chemistry
		Diffraction methods
			8.1 X-ray diffraction
			8.2 Neutron diffraction
		Absorption and emission spectroscopies
			8.3 Ultraviolet–visible spectroscopy
			8.4 Fluorescence or emission spectroscopy
			8.5 Infrared and Raman spectroscopy
		Resonance techniques
			8.6 Nuclear magnetic resonance
			8.7 Electron paramagnetic resonance
			8.8 Mössbauer spectroscopy
		Ionization-based techniques
			8.9 Photoelectron spectroscopy
			8.10 X-ray absorption spectroscopy
			8.11 Mass spectrometry
		Chemical analysis
			8.12 Atomic absorption spectroscopy
			8.13 CHN analysis
			8.14 X-ray fluorescence elemental analysis
			8.15 Thermal analysis
		Magnetometry and magnetic susceptibility
		Electrochemical techniques
		Microscopy
			8.16 Scanning probe microscopy
			8.17 Electron microscopy
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PART 2 The elements and their compounds
	9 Periodic trends
		Periodic properties of the elements
			9.1 Valence electron configurations
			9.2 Atomic parameters
			9.3 Occurrence
			9.4 Metallic character
			9.5 Oxidation states
		Periodic characteristics of compounds
			9.6 Presence of unpaired electrons
			9.7 Coordination numbers
			9.8 Bond enthalpy trends
			9.9 Binary compounds
			9.10 Wider aspects of periodicity
			9.11 Anomalous nature of the first member of each group
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	10 Hydrogen
		PART A: The essentials
			10.1 The element
			10.2 Simple compounds
		PART B: The detail
			10.3 Nuclear properties
			10.4 Production of dihydrogen
			10.5 Reactions of dihydrogen
			10.6 Compounds of hydrogen
			10.7 General methods for synthesis of binary hydrogen compounds
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	11 The Group 1 elements
		PART A: The essentials
			11.1 The elements
			11.2 Simple compounds
			11.3 The atypical properties of lithium
		PART B: The detail
			11.4 Occurrence and extraction
			11.5 Uses of the elements and their compounds
			11.6 Hydrides
			11.7 Halides
			11.8 Oxides and related compounds
			11.9 Sulfides, selenides, and tellurides
			11.10 Hydroxides
			11.11 Compounds of oxoacids
			11.12 Nitrides and carbides
			11.13 Solubility and hydration
			11.14 Solutions in liquid ammonia
			11.15 Zintl phases containing alkali metals
			11.16 Coordination compounds
			11.17 Organometallic compounds
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	12 The Group 2 elements
		PART A: The essentials
			12.1 The elements
			12.2 Simple compounds
			12.3 The anomalous properties of beryllium
		PART B: The detail
			12.4 Occurrence and extraction
			12.5 Uses of the elements and their compounds
			12.6 Hydrides
			12.7 Halides
			12.8 Oxides, sulfides, and hydroxides
			12.9 Nitrides and carbides
			12.10 Salts of oxoacids
			12.11 Solubility, hydration, and beryllates
			12.12 Coordination compounds
			12.13 Organometallic compounds
			12.14 Lower oxidation state Group 2 compounds
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	13 The Group 13 elements
		PART A: The essentials
			13.1 The elements
			13.2 Compounds
			13.3 Boron clusters and borides
		PART B: The detail
			13.4 Occurrence and recovery
			13.5 Uses of the elements and their compounds
			13.6 Simple hydrides of boron
			13.7 Boron trihalides
			13.8 Boron–oxygen compounds
			13.9 Compounds of boron with nitrogen
			13.10 Metal borides
			13.11 Higher boranes and borohydrides
			13.12 Metallaboranes and carboranes
			13.13 The hydrides of aluminium, gallium, indium, and thallium
			13.14 Trihalides of aluminium, gallium, indium, and thallium
			13.15 Low oxidation state halides of aluminium, gallium, indium, and thallium
			13.16 Oxo compounds of aluminium, gallium, indium, and thallium
			13.17 Sulfides of gallium, indium, and thallium
			13.18 Compounds with Group 15 elements
			13.19 Zintl phases
			13.20 Organometallic compounds
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	14 The Group 14 elements
		PART A: The essentials
			14.1 The elements
			14.2 Simple compounds
			14.3 Extended silicon–oxygen compounds
		PART B: The detail
			14.4 Occurrence and recovery
			14.5 Diamond and graphite
			14.6 Other forms of carbon
			14.7 Hydrides
			14.8 Compounds with halogens
			14.9 Compounds of carbon with oxygen and sulfur
			14.10 Simple compounds of silicon with oxygen
			14.11 Oxides of germanium, tin, and lead
			14.12 Compounds with nitrogen
			14.13 Carbides
			14.14 Silicides
			14.15 Extended silicon–oxygen compounds
			14.16 Organosilicon and organogermanium compounds
			14.17 Organometallic compounds
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	15 The Group 15 elements
		PART A: The essentials
			15.1 The elements
			15.2 Simple compounds
			15.3 Oxides and oxoanions of nitrogen
		PART B: The detail
			15.4 Occurrence and recovery
			15.5 Uses
			15.6 Nitrogen activation
			15.7 Nitrides and azides
			15.8 Phosphides
			15.9 Arsenides, antimonides, and bismuthides
			15.10 Hydrides
			15.11 Halides
			15.12 Oxohalides
			15.13 Oxides and oxoanions of nitrogen
			15.14 Oxides of phosphorus, arsenic, antimony, and bismuth
			15.15 Oxoanions of phosphorus, arsenic, antimony, and bismuth
			15.16 Condensed phosphates
			15.17 Phosphazenes
			15.18 Organometallic compounds of arsenic, antimony, and bismuth
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	16 The Group 16 elements
		PART A: The essentials
			16.1 The elements
			16.2 Simple compounds
			16.3 Ring and cluster compounds
		PART B: The detail
			16.4 Oxygen
			16.5 Reactivity of oxygen
			16.6 Sulfur
			16.7 Selenium, tellurium, and polonium
			16.8 Hydrides
			16.9 Halides
			16.10 Metal oxides
			16.11 Metal sulfides, selenides, tellurides, and polonides
			16.12 Oxides
			16.13 Oxoacids of sulfur
			16.14 Polyanions of sulfur, selenium, and tellurium
			16.15 Polycations of sulfur, selenium, and tellurium
			16.16 Sulfur–nitrogen compounds
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	17 The Group 17 elements
		PART A: The essentials
			17.1 The elements
			17.2 Simple compounds
			17.3 The interhalogens
		PART B: The detail
			17.4 Occurrence, recovery, and uses
			17.5 Molecular structure and properties
			17.6 Reactivity trends
			17.7 Pseudohalogens
			17.8 Special properties of fluorine compounds
			17.9 Structural features
			17.10 The interhalogens
			17.11 Halogen oxides
			17.12 Oxoacids and oxoanions
			17.13 Thermodynamic aspects of oxoanion redox reactions
			17.14 Trends in rates of oxoanion redox reactions
			17.15 Redox properties of individual oxidation states
			17.16 Fluorocarbons
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		EXERCISES
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	18 The Group 18 elements
		PART A: The essentials
			18.1 The elements
			18.2 Simple compounds
		PART B: The detail
			18.3 Occurrence and recovery
			18.4 Uses
			18.5 Synthesis and structure of xenon fluorides
			18.6 Reactions of xenon fluorides
			18.7 Xenon–oxygen compounds
			18.8 Xenon insertion compounds
			18.9 Organoxenon compounds
			18.10 Coordination compounds
			18.11 Other compounds of noble gases
		FURTHER READING
		EXERCISES
		TUTORIAL PROBLEMS
	19 The d-block elements
		PART A: The essentials
			19.1 Occurrence and recovery
			19.2 Chemical and physical properties
		PART B: The detail
			19.3 Group 3: scandium, yttrium, and lanthanum
			19.4 Group 4: titanium, zirconium, and hafnium
			19.5 Group 5: vanadium, niobium, and tantalum
			19.6 Group 6: chromium, molybdenum, and tungsten
			19.7 Group 7: manganese, technetium, and rhenium
			19.8 Group 8: iron, ruthenium, and osmium
			19.9 Group 9: cobalt, rhodium, and iridium
			19.10 Group 10: nickel, palladium, and platinum
			19.11 Group 11: copper, silver, and gold
			19.12 Group 12: zinc, cadmium, and mercury
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	20 d-Metal complexes:electronic structure and properties
		Electronic structure
			20.1 Crystal-field theory
			20.2 Ligand-field theory
		Electronic spectra
			20.3 Electronic spectra of atoms
			20.4 Electronic spectra of complexes
			20.5 Charge-transfer bands
			20.6 Selection rules and intensities
			20.7 Luminescence
		Magnetism
			20.8 Cooperative magnetism
			20.9 Spin-crossover complexes
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	21 Coordination chemistry: reactions of complexes
		Ligand substitution reactions
			21.1 Rates of ligand substitution
			21.2 The classification of mechanisms
		Ligand substitution in square-planar complexes
			21.3 The nucleophilicity of the entering group
			21.4 The shape of the transition state
		Ligand substitution in octahedral complexes
			21.5 Rate laws and their interpretation
			21.6 The activation of octahedral complexes
			21.7 Base hydrolysis
			21.8 Stereochemistry
			21.9 Isomerization reactions
		Redox reactions
			21.10 The classification of redox reactions
			21.11 The inner-sphere mechanism
			21.12 The outer-sphere mechanism
		Photochemical reactions
			21.13 Prompt and delayed reactions
			21.14 d–d and charge-transfer reactions
			21.15 Transitions in metal–metal bonded systems
		FURTHER READING
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		TUTORIAL PROBLEMS
	22 d-Metal organometallic chemistry
		Bonding
			22.1 Stable electron configurations
			22.2 Electron-count preference
			22.3 Electron counting and oxidation states
			22.4 Nomenclature
		Ligands
			22.5 Carbon monoxide
			22.6 Phosphines
			22.7 Hydrides and dihydrogen complexes
			22.8 η1-Alkyl, -alkenyl, -alkynyl, and -aryl ligands
			22.9 η2-Alkene and -alkyne ligands
			22.10 Nonconjugated diene and polyene ligands
			22.11 Butadiene, cyclobutadiene, and cyclooctatetraene
			22.12 Benzene and other arenes
			22.13 The allyl ligand
			22.14 Cyclopentadiene and cycloheptatriene
			22.15 Carbenes
			22.16 Alkanes, agostic hydrogens, and noble gases
			22.17 Dinitrogen and nitrogen monoxide
		Compounds
			22.18 d-Block carbonyls
			22.19 Metallocenes
			22.20 Metal–metal bonding and metal clusters
		Reactions
			22.21 Ligand substitution
			22.22 Oxidative addition and reductive elimination
			22.23 σ-Bond metathesis
			22.24 1,1-Migratory insertion reactions
			22.25 1,2-Insertions and β-hydride elimination
			22.26 α-, γ-, and δ-Hydride eliminations and cyclometallations
		Catalysis
			22.27 Alkene metathesis
			22.28 Hydrogenation of alkenes
			22.29 Hydroformylation
			22.30 Wacker oxidation of alkenes
			22.31 Palladium-catalysed C–C bond-forming reactions
			22.32 Oligomerization and polymerization
		FURTHER READING
		EXERCISES
		TUTORIAL PROBLEMS
	23 The f-block elements
		The elements
			23.1 The valence orbitals
			23.2 Occurrence and recovery
			23.3 Physical properties and applications
		Lanthanoid chemistry
			23.4 General trends
			23.5 Optical and magnetic properties
			23.6 Binary ionic compounds
			23.7 Ternary and complex oxides
			23.8 Coordination compounds
			23.9 Organometallic compounds
		Actinoid chemistry
			23.10 General trends
			23.11 Electronic spectra of the actinoids
			23.12 Thorium and uranium
			23.13 Neptunium, plutonium, and americium
		FURTHER READING
		EXERCISES
		TUTORIAL PROBLEMS
PART3 Expanding ourhorizons: advances and applications
	24 Materials chemistry and nanomaterials
		Synthesis of materials
			24.1 The formation of bulk materials
		Defects and ion transport
			24.2 Extended defects
			24.3 Atom and ion diffusion
			24.4 Solid electrolytes
		Metal oxides, nitrides, and fluorides
			24.5 Monoxides of the 3d metals
			24.6 Higher oxides and complex oxides
			24.7 Oxide glasses
			24.8 Nitrides, fluorides, and mixed-anion phases
		Sulfides, intercalation compounds, and metal-rich phases
			24.9 Layered MS2 compounds and intercalation
			24.10 Chevrel phases and chalcogenide thermoelectrics
		Framework structures and heterogeneous catalysis in porous materials
			24.11 Structures based on tetrahedral oxoanions
			24.12 Structures based on linked octahedral and tetrahedral metal centres
			24.13 Zeolites and microporous structures in heterogeneous catalysis
		Hydrides and hydrogen-storage materials
			24.14 Metal hydrides
			24.15 Other inorganic hydrogen-storage materials
		Optical properties of inorganic materials
			24.16 Coloured solids
			24.17 White and black pigments
			24.18 Photocatalysts
		Semiconductor chemistry
			24.19 Group 14 semiconductors
			24.20 Semiconductor systems isoelectronic with silicon
		Molecular materials and fullerides
			24.21 Fullerides
			24.22 Molecular materials chemistry
		Nanomaterials
			24.23 Nanomaterial terminology and history
			24.24 Solution-based synthesis of nanoparticles
			24.25 Vapour-phase synthesis of nanoparticles via solutions or solids
			24.26 Templated synthesis of nanomaterials using frameworks, supports, and substrates
			24.27 Characterization and formation of nanomaterials using microscopy
		Nanostructures and properties
			24.28 One-dimensional control: carbon nanotubes and inorganic nanowires
			24.29 Two-dimensional control: graphene, quantum wells, and solid-state superlattices
			24.30 Three-dimensional control: mesoporous materials and composites
			24.31 Special optical properties of nanomaterials
		Heterogeneous nanoparticle catalysts
			24.32 The nature of heterogeneous catalysts
			24.33 Reactions involving heterogeneousnanoparticle catalysts
		FURTHER READING
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	25 Green chemistry
		Twelve principles
			25.1 Prevention
			25.2 Atom economy
			25.3 Less hazardous chemical species
			25.4 Designing safer chemicals
			25.5 Safer solvents and auxiliaries
			25.6 Design for energy efficiency
			25.7 Use of renewable feedstocks
			25.8 Reduce derivatives
			25.9 Catalysis
			25.10 Design for degradation
			25.11 Real-time analysis for pollution prevention
			25.12 Inherently safer chemistry for accident prevention
		FURTHER READING
		EXERCISES
		TUTORIAL PROBLEMS
	25 Biological inorganicchemistry
		Twelve principles
			25.1 Prevention
			25.2 Atom economy
			25.3 Less hazardous chemical species
			25.4 Designing safer chemicals
			25.5 Safer solvents and auxiliaries
			25.6 Design for energy efficiency
			25.7 Use of renewable feedstocks
			25.8 Reduce derivatives
			25.9 Catalysis
			25.10 Design for degradation
			25.11 Real-time analysis for pollution prevention
			25.12 Inherently safer chemistry for accident prevention
		FURTHER READING
		EXERCISES
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	26 Biological inorganic chemistry
		The organization of cells
			26.1 The physical structure of cells
			26.2 The inorganic composition of living organisms
			26.3 Biological metal-coordination sites
		Metal ions in transport and communication
			26.4 Sodium and potassium transport
			26.5 Calcium signalling proteins
			26.6 Selective transport and storage of iron
			26.7 Oxygen transport and storage
			26.8 Electron transfer
		Catalytic processes
			26.9 Acid–base catalysis
			26.10 Enzymes dealing with H2O2 and O2
			26.11 Enzymes dealing with radicals and alkyl groups
			26.12 Oxygen atom transfer by molybdenum and tungsten enzymes
			26.13 Hydrogenases, enzymes that activate H2
			26.14 The nitrogen cycle
		Metals in gene regulation
			27.15 Transcription factors and the role of Zn
			26.16 Iron proteins as sensors
			26.17 Proteins that sense Cu and Zn levels
			26.18 Biomineralization
		Perspectives
			26.19 The contributions of individual elements
			26.20 Future directions
		FURTHER READING
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	27 Inorganic chemistry in medicine
		The chemistry of elements in medicine
			27.1 Inorganic complexes in cancer treatment
			27.2 Anti-arthritis drugs
			27.3 Bismuth in the treatment of gastric ulcers
			27.4 Lithium in the treatment of bipolardis orders
			27.5 Organometallic drugs in the treatment of malaria
			27.6 Metal complexes as antiviral agents
			27.7 Metal drugs that slowly release CO: an agent against post-operative stress
			27.8 Chelation therapy
			27.9 Imaging agents
			27.10 Nanoparticles in directed drug delivery
		FURTHER READING
		EXERCISES
		TUTORIAL PROBLEMS
Resource section 1
Resource section 2
Resource section 3
Resource section 4
Resource section 5
Resource section 6
Index
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