CATHERINE E. HOUSECROFT & ALAN G. SHARPE INORGANIC ...

INORGANIC CHEMISTRY

CATHERINE E. HOUSECROFT & ALAN G. SHARPE

FIFTH EDITION

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INORGANIC CHEMISTRYFIFTH EDITION

Inorganic Chemistry eBook

Table of Contents

Front Cover

IFC

Periodic Table

Title Page

Copyright Page

Summary of Contents

Contents

Guided tour

Preface to the fifth edition

Acknowledgements

1 Basic concepts: atoms 1.1 Introduction

Inorganic chemistry: it is not an isolated branch of chemistry

The aims of Chapters 1 and 2

1.2 Fundamental particles of an atom

1.3 Atomic number, mass number and isotopes Nuclides, atomic number and mass number

Relative atomic mass

Isotopes

1.4 Successes in early quantum theory Some important successes of classical quantum theory

Bohrs theory of the atomic spectrum of hydrogen

1.5 An introduction to wave mechanics The wave-nature of electrons

The uncertainty principle

The Schrodinger wave equation

1.6 Atomic orbitals The quantum numbers n , l and ml

The radial part of the wavefunction, R (r )

The radial distribution function, 4�r2R(r)2

The angular part of the wavefunction, A.�; �.

Orbital energies in a hydrogen-like species

Size of orbitals

The spin quantum number and the magnetic spin quantum number

The ground state of the hydrogen atom

1.7 Many-electron atoms

Table of Contents

The helium atom: two electrons

Ground state electronic configurations: experimental data

Penetration and shielding

1.8 The periodic table

1.9 The aufbau principle Ground state electronic configurations

Valence and core electrons

Diagrammatic representations of electronic configurations

1.10 Ionization energies and electron affinities Ionization energies

Electron affinities

2 Basic concepts: molecules 2.1 Bonding models: an introduction

A historical overview

Lewis structures

2.2 Homonuclear diatomic molecules: valence bond (VB) theory Uses of the term homonuclear

Covalent bond distance, covalent radius and van der Waals radius

The valence bond (VB) model of bonding in H2

The valence bond (VB) model applied to F2 , O2 and N2

2.3 Homonuclear diatomic molecules: molecular orbital (MO) theoryAn overview of the MO model

Molecular orbital theory applied to the bonding in H2

The bonding in He2; Li2 and Be2

The bonding in F2 and O2

What happens if the sp separation is small?

2.4 The octet rule and isoelectronic speciesThe octet rule: first row p-block elements

Isoelectronic species

The octet rule: heavier p-block elements

2.5 Electronegativity valuesPauling electronegativity values, �P

Mulliken electronegativity values, �M

AllredRochow electronegativity values, �AR

Electronegativity: final remarks

2.6 Dipole momentsPolar diatomic molecules

Molecular dipole moments

2.7 MO theory: heteronuclear diatomic moleculesWhich orbital interactions should be considered?

Hydrogen fluoride

Table of Contents

Carbon monoxide

2.8 Molecular shape and the VSEPR modelValence-shell electron-pair repulsion model

Structures derived from a trigonal bipyramid

Limitations of the VSEPR model

2.9 Molecular shape: stereoisomerismSquare planar species

Octahedral species

Trigonal bipyramidal species

High coordination numbers

Double bonds

3 Introduction to molecular symmetry3.1 Introduction

3.2 Symmetry operations and symmetry elementsRotation about an n-fold axis of symmetry

Reflection through a plane of symmetry (mirror plane)

Reflection through a centre of symmetry (inversion centre)

Rotation about an axis, followed by reflection through a plane perpendicular to

this axis

Identity operator

3.3 Successive operations

3.4 Point groups C1 point group

C1v point group

D1h point group

Td, Oh or Ih point groups

Determining the point group of a molecule or molecular ion

3.5 Character tables: an introduction

3.6 Why do we need to recognize symmetry elements?

3.7 Vibrational spectroscopy How many vibrational modes are there for a given molecular species?

Selection rules for an infrared or Raman active mode of vibration

Linear (D1h or C1v ) and bent (C2v ) triatomic molecules

Bent molecules XY2 : using the C2v character table

XY3 molecules with D3h symmetry

XY3 molecules with C3v symmetry

XY4 molecules with Td or D4h symmetry

XY6 molecules with Oh symmetry

Metal carbonyl complexes, M(CO)n

Metal carbonyl complexes M(CO)6�n Xn

Observing IR spectroscopic absorptions

Table of Contents

3.8 Chiral molecules

4 Experimental techniques 4.1 Introduction

4.2 Separation and purification techniques Gas chromatography (GC)

Liquid chromatography (LC)

High-performance liquid chromatography (HPLC)

Recrystallization

4.3 Elemental analysis CHN analysis by combustion

Atomic absorption spectroscopy (AAS)

4.4 Compositional analysis: thermogravimetry (TG)

4.5 Mass spectrometry Electron ionization (EI)

Fast atom bombardment (FAB)

Matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF)

Electrospray ionization (ESI)

4.6 Infrared and Raman spectroscopies Energies and wavenumbers of molecular vibrations

The Fourier transform infrared (FT-IR) spectrometer and sample preparation

Diagnostic absorptions

Deuterium/hydrogen exchange

Raman spectroscopy

4.7 Electronic spectroscopyUV-VIS absorption spectroscopy

Types of absorption

Absorbance and the BeerLambert Law

Emission spectroscopy

4.8 Nuclear magnetic resonance (NMR) spectroscopy NMR active nuclei and isotope abundance

Which nuclei are suitable for NMR spectroscopic studies?

Resonance frequencies and chemical shifts

Chemical shift ranges

Solvents for solution studies

Integration of signals and signal broadening

Homonuclear spinspin coupling: 1 H1 H

Heteronuclear spinspin coupling: 13 C1 H

Case studies

Stereochemically non-rigid species

Exchange processes in solution

4.9 Electron paramagnetic resonance (EPR) spectroscopy

Table of Contents

What is EPR spectroscopy?

The Zeeman electronic effect

EPR spectra

4.10 Mo¨ssbauer spectroscopy The technique of MoÅN ssbauer spectroscopy

What can isomer shift data tell us?

4.11 Structure determination: diffraction methods X-ray diffraction (XRD)

Single crystal X-ray diffraction

Powder X-ray diffraction

Single crystal neutron diffraction

Electron diffraction

Low-energy electron diffraction (LEED)

Structural databases

4.12 Photoelectron spectroscopy (PES, UPS, XPS, ESCA)

4.13 Computational methods HartreeFock theory

Density functional theory

Hu¨ckel MO theory

Molecular mechanics (MM)

5 Bonding in polyatomic molecules 5.1 Introduction

5.2 Valence bond theory: hybridization of atomic orbitals What is orbital hybridization?

sp Hybridization: a scheme for linear species

sp2 Hybridization: a scheme for trigonal planar species

sp3 Hybridization: a scheme for tetrahedral and related species

Other hybridization schemes

5.3 Valence bond theory: multiple bonding in polyatomic molecules C2 H4

HCN

BF3

5.4 Natural bond orbitals

5.5 Molecular orbital theory: the ligand group orbital approach and Molecular orbital diagrams: moving from a diatomic to polyatomic species

MO approach to bonding in linear XH2 : symmetry matching by inspection

MO approach to bonding in linear XH2 : working from molecular symmetry

A bent triatomic: H2 O

5.6 Molecular orbital theory applied to the polyatomic molecules BH3 , NH3 andCH4

Table of Contents

BH3

NH3

CH4

A comparison of the MO and VB bonding models

5.7 Molecular orbital theory: bonding analyses soon become complicated

5.8 Molecular orbital theory: learning to use the theory objectively -Bondingin CO2

p-Bonding in CO2

.NO3

SF6

Three-centre two-electron interactions

A more advanced problem: B2 H6

6 Structures and energetics of metallic and ionic solids 6.1 Introduction

6.2 Packing of spheres Cubic and hexagonal close-packing

The unit cell: hexagonal and cubic close-packing

Interstitial holes: hexagonal and cubic close-packing

Non-close-packing: simple cubic and body-centred cubic arrays

6.3 The packing-of-spheres model applied to the structures of elements Group 18 elements in the solid state

H2 and F2 in the solid state

Metallic elements in the solid state

6.4 Polymorphism in metals Polymorphism: phase changes in the solid state

Phase diagrams

6.5 Metallic radii

6.6 Melting points and standard enthalpies of atomization of metals

6.7 Alloys and intermetallic compounds Substitutional alloys

Interstitial alloys

Intermetallic compounds

6.8 Bonding in metals and semiconductorsElectrical conductivity and resistivity

Band theory of metals and insulators

The Fermi level

6.9 Semiconductors Intrinsic semiconductors

Extrinsic (n- and p-type) semiconductors

6.10 Sizes of ions

Table of Contents

Ionic radii

Periodic trends in ionic radii

6.11 Ionic lattices The rock salt (NaCl) structure type

The caesium chloride (CsCl) structure type

The fluorite (CaF2) structure type

The antifluorite structure type

The zinc blende (ZnS) structure type: a diamond-type network

The b -cristobalite (SiO2) structure type

The wurtzite (ZnS) structure type

The rutile (TiO2) structure type

CdI2 and CdCl2 : layer structures

The perovskite (CaTiO3) structure type: a double oxide

6.12 Crystal structures of semiconductors

6.13 Lattice energy: estimates from an electrostatic model Coulombic attraction within an isolated ion-pair

Coulombic interactions in an ionic lattice

Born forces

The BornLandeÅL equation

Madelung constants

Refinements to the BornLandeÅL equation

Overview

6.14 Lattice energy: the BornHaber cycle

6.15 Lattice energy: calculated versus experimental values

6.16 Estimating lattice energies of new materials The Kapustinskii equation

The volume-based thermodynamic (VBT) approach

6.17 Applications of lattice energies Estimation of electron affinities

Fluoride affinities

Estimation of standard enthalpies of formation and disproportionation

6.18 Defects in solid state lattices Schottky defect

Frenkel defect

Experimental observation of Schottky and Frenkel defects

Non-stoichiometric compounds

Colour centres (F-centres)

Thermodynamic effects of crystal defects

7 Acids, bases and ions in aqueous solution 7.1 Introduction

7.2 Properties of water

Table of Contents

Structure and hydrogen bonding

The self-ionization of water

Water as a Bronsted acid or base

7.3 Definitions and units in aqueous solution Molarity and molality

Standard state

Activity

7.4 Some Brønsted acids and basesCarboxylic acids: examples of mono-, di- and polybasic acids

Inorganic acids

Inorganic bases: hydroxides

Inorganic bases: nitrogen bases

7.5 The energetics of acid dissociation in aqueous solution Hydrogen halides

H2 S; H2 Se and H2 Te

7.6 Trends within a series of oxoacids EOn (OH)m

7.7 Aquated cations: formation and acidic properties Water as a Lewis base

Aquated cations as Bronsted acids

7.8 Amphoteric oxides and hydroxides Amphoteric behaviour

Periodic trends in amphoteric properties

7.9 Solubilities of ionic salts Solubility and saturated solutions

Sparingly soluble salts and solubility products

The energetics of the dissolution of an ionic salt: �solG

The energetics of the dissolution of an ionic salt: hydration of ions

Solubilities: some concluding remarks

7.10 Common-ion effect

7.11 Coordination complexes: an introduction Definitions and terminology

Investigating coordination complex formation

7.12 Stability constants of coordination complexes Determination of stability constants

Trends in stepwise stability constants

Thermodynamic considerations of complex formation: an introduction

7.13 Factors affecting the stabilities of complexes containing only monodentateligands

Ionic size and charge

Hard and soft metal centres and ligands

8 Reduction and oxidation

Table of Contents

8.1 Introduction Oxidation and reduction

Oxidation states

Stock nomenclature

8.2 Standard reduction potentials, Eo , and relationships between Eo ,�Go andK

Half-cells and galvanic cells

Defining and using standard reduction potentials, E

Dependence of reduction potentials on cell conditions

8.3 The effect of complex formation or precipitation on Mz+/M reductionpotentials

Half-cells involving silver halides

Modifying the relative stabilities of different oxidation states of a metal

8.4 Disproportionation reactions Disproportionation

Stabilizing species against disproportionation

8.5 Potential diagrams

8.6 FrostEbsworth diagramsFrostEbsworth diagrams and their relationship to potential diagrams

Interpretation of FrostEbsworth diagrams

8.7 The relationships between standard reduction potentials and some otherquantities

Factors influencing the magnitudes of standard reduction potentials

Values of �fG for aqueous ions

8.8 Applications of redox reactions to the extraction of elements from theirores

Ellingham diagrams

9 Non-aqueous media 9.1 Introduction

9.2 Relative permittivity

9.3 Energetics of ionic salt transfer from water to an organic solvent

9.4 Acidbase behaviour in non-aqueous solvents Strengths of acids and bases

Levelling and differentiating effects

Acids in acidic solvents

Acids and bases: a solvent-oriented definition

Proton-containing and aprotic solvents

9.5 Liquid sulfur dioxide

9.6 Liquid ammonia Physical properties

Table of Contents

Self-ionization

Reactions in liquid NH3

Solutions of s-block metals in liquid NH3

Redox reactions in liquid NH3

9.7 Liquid hydrogen fluoride Physical properties

Acidbase behaviour in liquid HF

Electrolysis in liquid HF

9.8 Sulfuric acid and fluorosulfonic acid Physical properties of sulfuric acid

Acidbase behaviour in liquid H2 SO4

Physical properties of fluorosulfonic acid

9.9 Superacids

9.10 Bromine trifluoridePhysical properties

Behaviour of fluoride salts and molecular fluorides in BrF3

Reactions in BrF3

9.11 Dinitrogen tetraoxide Physical properties

Reactions in N2 O4

9.12 Ionic liquids Molten salt solvent systems

Ionic liquids at ambient temperatures

9.13 Supercritical fluids Properties of supercritical fluids and their uses as solvents

Supercritical fluids as media for inorganic chemistry

10 Hydrogen 10.1 Hydrogen: the simplest atom

10.2 The H. and H� ions The hydrogen ion (proton)

The hydride ion

10.3 Isotopes of hydrogen Protium and deuterium

Kinetic isotope effects

Deuterated compounds

Tritium

10.4 Dihydrogen Occurrence

Physical properties

Synthesis and uses

Table of Contents

Reactivity

10.5 Polar and non-polar EH bonds

10.6 Hydrogen bonding The hydrogen bond

Trends in boiling points, melting points and enthalpies of vaporization for p

-block binary hydrides

Infrared spectroscopy

Solid state structures

Hydrogen bonding in biological systems

10.7 Binary hydrides: classification and general propertiesClassification

Metallic hydrides

Saline hydrides

Molecular hydrides and complexes derived from them

Covalent hydrides with extended structures

11 Group 1: the alkali metals 11.1 Introduction

11.2 Occurrence, extraction and uses Occurrence

Extraction

Major uses of the alkali metals and their compounds

11.3 Physical properties General properties

Atomic spectra and flame tests

Radioactive isotopes

NMR active nuclei

11.4 The metals Appearance

Reactivity

11.5 Halides

11.6 Oxides and hydroxides Oxides, peroxides, superoxides, suboxides and ozonides

Hydroxides

11.7 Salts of oxoacids: carbonates and hydrogencarbonates

11.8 Aqueous solution chemistry and macrocyclic complexes Hydrated ions

Complex ions

11.9 Non-aqueous coordination chemistry

12 The group 2 metals 12.1 Introduction

Table of Contents


Extraction

Major uses of the group 2 metals and their compounds

12.3 Physical properties General properties

Flame tests


12.4 The metals Appearance

Reactivity

12.5 Halides Beryllium halides

Halides of Mg, Ca, Sr and Ba

12.6 Oxides and hydroxides Oxides and peroxides

Hydroxides

12.7 Salts of oxoacids

12.8 Complex ions in aqueous solution Aqua species of beryllium

Aqua species of Mg2+, Ca2+, Sr2+ and Ba2+

Complexes with ligands other than water

12.9 Complexes with amido or alkoxy ligands

12.10 Diagonal relationships between Li and Mg, and between Be and Al Lithium and magnesium

Beryllium and aluminium

13 The group 13 elements 13.1 Introduction


Extraction

Major uses of the group 13 elements and their compounds

13.3 Physical properties Electronic configurations and oxidation states

NMR active nuclei

13.4 The elements Appearance

Structures of the elements

Reactivity

13.5 Simple hydrides

Table of Contents

Neutral hydrides

The [MH4]- ions

13.6 Halides and complex halides Boron halides: BX3 and B2 X4

Al(III), Ga(III), In(III) and Tl(III) halides and their complexes

Lower oxidation state Al, Ga, In and Tl halides

13.7 Oxides, oxoacids, oxoanions and hydroxides Boron oxides, oxoacids and oxoanions

Aluminium oxides, oxoacids, oxoanions and hydroxides

Oxides of Ga, In and Tl

13.8 Compounds containing nitrogen Nitrides

Ternary boron nitrides

Molecular species containing BN or BP bonds

Molecular species containing group 13 metalnitrogen bonds

13.9 Aluminium to thallium: salts of oxoacids, aqueous solution chemistry andcomplexes

Aluminium sulfate and alums

Aqua ions

Redox reactions in aqueous solution

Coordination complexes of the M3+ ions

13.10 Metal borides

13.11 Electron-deficient borane and carbaborane clusters: an introduction



Extraction and manufacture

Uses

14.3 Physical properties Ionization energies and cation formation

Some energetic and bonding considerations

NMR active nuclei

Mossbauer spectroscopy

14.4 Allotropes of carbon Graphite and diamond: structure and properties

Graphite: intercalation compounds

Fullerenes: synthesis and structure

Fullerenes: reactivity

Carbon nanotubes

14.5 Structural and chemical properties of silicon, germanium, tin and lead

Table of Contents

Structures

Chemical properties

14.6 Hydrides Binary hydrides

Halohydrides of silicon and germanium

14.7 Carbides, silicides, germides, stannides and plumbides Carbides

Silicides

Zintl ions containing Si, Ge, Sn and Pb

14.8 Halides and complex halides Carbon halides

Silicon halides

Halides of germanium, tin and lead

14.9 Oxides, oxoacids and hydroxides Oxides and oxoacids of carbon

Silica, silicates and aluminosilicates

Oxides, hydroxides and oxoacids of germanium, tin and lead

14.10 Siloxanes and polysiloxanes (silicones)

14.11 Sulfides

14.12 Cyanogen, silicon nitride and tin nitride Cyanogen and its derivatives

Silicon nitride

Tin(IV) nitride

14.13 Aqueous solution chemistry and salts of oxoacids of germanium, tin andlead



Extraction

Uses

15.3 Physical properties Bonding considerations

NMR active nuclei


15.4 The elements Nitrogen

Phosphorus

Arsenic, antimony and bismuth

15.5 Hydrides

Table of Contents

Trihydrides, EH3 (E. N, P, As, Sb and Bi)

Hydrides E2 H4 (E. N, P, As)

Chloramine and hydroxylamine

Hydrogen azide and azide salts

15.6 Nitrides, phosphides, arsenides, antimonides and bismuthides Nitrides

Phosphides

Arsenides, antimonides and bismuthides

15.7 Halides, oxohalides and complex halides Nitrogen halides

Oxofluorides and oxochlorides of nitrogen

Phosphorus halides

Phosphoryl trichloride, POCl3

Arsenic and antimony halides

Bismuth halides

15.8 Oxides of nitrogen Dinitrogen monoxide, N2O

Nitrogen monoxide, NO

Dinitrogen trioxide, N2O3

Dinitrogen tetraoxide, N2 O4 , and nitrogen dioxide, NO2

Dinitrogen pentaoxide, N2O5

15.9 Oxoacids of nitrogen Isomers of H2 N2 O2

Nitrous acid, HNO2

Nitric acid, HNO3 , and its derivatives

15.10 Oxides of phosphorus, arsenic, antimony and bismuth Oxides of phosphorus

Oxides of arsenic, antimony and bismuth

15.11 Oxoacids of phosphorus Phosphinic acid, H3 PO2

Phosphonic acid, H3 PO3

Hypodiphosphoric acid, H4 P2 O6

Phosphoric acid, H3 PO4 , and its derivatives

Chiral phosphate anions

15.12 Oxoacids of arsenic, antimony and bismuth

15.13 Phosphazenes

15.14 Sulfides and selenides Sulfides and selenides of phosphorus

Arsenic, antimony and bismuth sulfides

15.15 Aqueous solution chemistry and complexes

16 The group 16 elements

Table of Contents

16.1 Introduction


Extraction

Uses

16.3 Physical properties and bonding considerations NMR active nuclei and isotopes as tracers

16.4 The elements Dioxygen

Ozone

Sulfur: allotropes

Sulfur: reactivity

Selenium and tellurium

16.5 Hydrides Water, H2O

Hydrogen peroxide, H2O2

Hydrides H2E (E = S, Se, Te)

Polysulfanes

16.6 Metal sulfides, polysulfides, polyselenides and polytellurides Sulfides

Polysulfides

Polyselenides and polytellurides

16.7 Halides, oxohalides and complex halides Oxygen fluorides

Sulfur fluorides and oxofluorides

Sulfur chlorides and oxochlorides

Halides of selenium and tellurium

16.8 Oxides Oxides of sulfur

Oxides of selenium and tellurium

16.9 Oxoacids and their salts Dithionous acid, H2S2O4

Sulfurous and disulfurous acids, H2SO3 and H2S2O5

Dithionic acid, H2S2O6

Sulfuric acid, H2SO4

Fluoro- and chlorosulfonic acids, HSO3F and HSO3 Cl

Polyoxoacids with SOS units

Peroxysulfuric acids, H2S2O8 and H2SO5

Thiosulfuric acid, H2S2O3, and polythionates

Oxoacids of selenium and tellurium

16.10 Compounds of sulfur and selenium with nitrogen

Table of Contents

Sulfurnitrogen compounds

Tetraselenium tetranitride

16.11 Aqueous solution chemistry of sulfur, selenium and tellurium


Fluorine, chlorine, bromine and iodine

Astatine and tennessine


Extraction

Uses

17.3 Physical properties and bonding considerations NMR active nuclei and isotopes as tracers

17.4 The elements Difluorine

Dichlorine, dibromine and diiodine

Charge transfer complexes

Clathrates

17.5 Hydrogen halides

17.6 Metal halides: structures and energetics

17.7 Interhalogen compounds and polyhalogen ions Interhalogen compounds

Bonding in . [XY2]- ions

Polyhalogen cations

Polyhalide anions

17.8 Oxides and oxofluorides of chlorine, bromine and iodine Oxides

Oxofluorides

17.9 Oxoacids and their salts Hypofluorous acid, HOF

Oxoacids of chlorine, bromine and iodine

17.10 Aqueous solution chemist



Extraction

Uses

18.3 Physical properties NMR active nuclei

Table of Contents

18.4 Compounds of xenon Fluorides

Chlorides

Oxides

Oxofluorides and oxochlorides

Other compounds of xenon

18.5 Compounds of argon, krypton and radon

19 d-Block metal chemistry: general considerations 19.1 Topic overview

19.2 Ground state electronic configurationsd-Block metals versus transition elements

Electronic configurations

19.3 Physical properties

19.4 The reactivity of the metals

19.5 Characteristic properties: a general perspective Colour

Paramagnetism

Complex formation

Variable oxidation states

19.6 Electroneutrality principle

19.7 Coordination numbers and geometries The Kepert model

Coordination numbers in the solid state

Coordination number 2








Coordination numbers of 10 and above

19.8 Isomerism in d -block metal complexes Structural isomerism: ionization isomers

Structural isomerism: hydration isomers

Structural isomerism: coordination isomerism

Structural isomerism: linkage isomerism

Stereoisomerism: diastereoisomers

Stereoisomerism: enantiomers

20 d-Block metal chemistry: coordination complexes

Table of Contents

20.1 Introduction High- and low-spin states

20.2 Bonding in d -block metal complexes: valence bond theory Hybridization schemes

20.3 Crystal field theory The octahedral crystal field

Crystal field stabilization energy: high- and low-spin octahedral complexes

JahnTeller distortions

The tetrahedral crystal field

The square planar crystal field

Other crystal fields

Crystal field theory: uses and limitations

20.4 Molecular orbital theory: octahedral complexes Complexes with no metalligand � -bonding

Complexes with metalligand � -bonding

20.5 Ligand field theory

20.6 Describing electrons in multi-electron systems Quantum numbers L and ML for multi-electron species

Quantum numbers S and MS for multi-electron species

Microstates and term symbols

The quantum numbers J and MJ

Ground states of elements with Z=1-�10

The d2 configuration

20.7 Electronic spectra: absorption Spectral features

Charge transfer absorptions

Selection rules

Electronic absorption spectra of octahedral and tetrahedral complexes

Interpretation of electronic absorption spectra: use of Racah parameters

Interpretation of electronic absorption spectra: TanabeSugano diagrams

20.8 Electronic spectra: emission

20.9 Evidence for metalligand covalent bonding The nephelauxetic effect

EPR spectroscopy

20.10 Magnetic properties Magnetic susceptibility and the spin-only formula

Spin and orbital contributions to the magnetic moment

The effects of temperature on �eff

Spin crossover

Ferromagnetism, antiferromagnetism and ferrimagnetism

20.11 Thermodynamic aspects: ligand field stabilization energies (LFSE)

Table of Contents

Trends in LFSE

Lattice energies and hydration energies of Mn+ ions

Octahedral versus tetrahedral coordination: spinels

20.12 Thermodynamic aspects: the IrvingWilliams series

20.13 Thermodynamic aspects: oxidation states in aqueous solution

21 d-Block metal chemistry: the first row metals21.1 Introduction

21.2 Occurrence, extraction and uses

21.3 Physical properties: an overview

21.4 Group 3: scandium The metal

Scandium(III)

21.5 Group 4: titanium The metal

Titanium(IV)

Titanium(III)

Low oxidation states

21.6 Group 5: vanadium The metal

Vanadium(V)

Vanadium(IV)

Vanadium(III)

Vanadium(II)

21.7 Group 6: chromium The metal

Chromium(VI)

Chromium(V) and chromium(IV)

Chromium(III)

Chromium(II)

Chromiumchromium multiple bonds

21.8 Group 7: manganese The metal

Manganese(VII)

Manganese(VI)

Manganese(V)

Manganese(IV)

Manganese(III)

Manganese(II)

Manganese(I)

21.9 Group 8: iron

Table of Contents

The metal

Iron(VI), iron(V) and iron(IV)

Iron(III)

Iron(II)

Iron in low oxidation states

21.10 Group 9: cobalt The metal

Cobalt(IV)

Cobalt(III)

Cobalt(II)

21.11 Group 10: nickel The metal

Nickel(IV) and nickel(III

Nickel(II)

Nickel(I)

21.12 Group 11: copper The metal

Copper(IV) and copper(III)

Copper(II)

Copper(I)

21.13 Group 12: zinc The metal

Zinc(II)

Zinc(I)

22 d-Block metal chemistry: the heavier metals 22.1 Introduction

22.2 Occurrence, extraction and uses

22.3 Physical properties Effects of the lanthanoid contraction

Coordination numbers

NMR active nuclei

22.4 Group 3: yttriumThe metal

Yttrium(III)

22.5 Group 4: zirconium and hafniumThe metals

Zirconium(IV) and hafnium(IV)

Lower oxidation states of zirconium and hafnium

Zirconium clusters

22.6 Group 5: niobium and tantalum

Table of Contents

The metals

Niobium(V) and tantalum(V)

Niobium(IV) and tantalum(IV)

Lower oxidation state halides

22.7 Group 6: molybdenum and tungsten The metals

Molybdenum(VI) and tungsten(VI)

Molybdenum(V) and tungsten(V)

Molybdenum(IV) and tungsten(IV)

Molybdenum(III) and tungsten(III)

Molybdenum(II) and tungsten(II)

22.8 Group 7: technetium and rhenium The metals

High oxidation states of technetium and rhenium: M(VII), M(VI) and M(V)

Technetium(IV) and rhenium(IV)

Technetium(III) and rhenium(III)

Technetium(I) and rhenium(I)

22.9 Group 8: ruthenium and osmiumThe metals

High oxidation states of ruthenium and osmium: M(VIII), M(VII) and M(VI)

Ruthenium(V), (IV) and osmium(V), (IV)

Ruthenium(III) and osmium(III)

Ruthenium(II) and osmium(II)

Mixed-valence ruthenium complexes

22.10 Group 9: rhodium and iridiumThe metals

High oxidation states of rhodium and iridium: M(VI) and M(V)

Rhodium(IV) and iridium(IV)

Rhodium(III) and iridium(III)

Rhodium(II) and iridium(II)

Rhodium(I) and iridium(I)

22.11 Group 10: palladium and platinumThe metals

The highest oxidation states: M(VI) and M(V)

Palladium(IV) and platinum(IV)

Palladium(III), platinum(III) and mixed-valence complexes

Palladium(II) and platinum(II)

Platinum(II)

22.12 Group 11: silver and goldThe metals

Gold(V) and silver(V)

Table of Contents

Gold(III) and silver(III)

Gold(II) and silver(II)

Gold(I) and silver(I)

Gold(I) and silver(I)

22.13 Group 12: cadmium and mercuryThe metals

Cadmium(II)

Mercury(II)

Mercury(I)

23 Organometallic compounds of s- and p-block elements23.1 Introduction

23.2 Group 1: alkali metal organometallics

23.3 Group 2 organometallics Beryllium

Magnesium

Calcium, strontium and barium

23.4 Group 13Boron

Aluminium

Gallium, indium and thallium

23.5 Group 14 Silicon

Germanium

Tin

Lead

Coparallel and tilted C5 -rings in group 14 metallocenes

23.6 Group 15 Bonding aspects and E=E bond formation

Arsenic, antimony and bismuth

23.7 Group 16 Selenium and tellurium

24 Organometallic compounds of d-block elements24.1 Introduction

24.2 Common types of ligand: bonding and spectroscopy �-Bonded alkyl, aryl and related ligands

Carbonyl ligands

Hydride ligands

Phosphane and related ligands

�-Bonded organic ligands

Nitrogen monoxide

Table of Contents

Dinitrogen

Dihydrogen

24.3 The 18-electron rule

24.4 Covalent bond classification (CBC)

24.5 Metal carbonyls: synthesis, physical properties and structureSynthesis and physical properties

Structures

24.6 The isolobal principle and application of Wades rules

24.7 Total valence electron counts in d-block organometallic clustersSingle cage structures

Condensed cages

Limitations of total valence counting schemes

24.8 Types of organometallic reactionsSubstitution of CO ligands

Oxidative addition

Alkyl and hydrogen migrations

b-Hydrogen elimination

a-Hydrogen abstraction

Summary

24.9 Metal carbonyls: selected reactions

24.10 Metal carbonyl hydrides and halides

24.11 Alkyl, aryl, alkene and alkyne complexes�-Bonded alkyl and aryl ligands

Alkene ligands

Alkyne ligands

24.12 Allyl and buta-1,3-diene complexes Allyl and related ligands

Buta-1,3-diene and related ligands

24.13 Carbene and carbyne complexes

24.14 Complexes containing Z5 -cyclopentadienyl ligandsFerrocene and other metallocenes

(Z5-Cp)2Fe2(CO)4 and derivatives

24.15 Complexes containing Z6- and Z7-ligandsZ6-Arene ligands

Cycloheptatriene and derived ligands

24.16 Complexes containing the Z4-cyclobutadiene ligand

25 Catalysis and some industrial processes25.1 Introduction and definitions

25.2 Catalysis: introductory conceptsEnergy profiles for a reaction: catalysed versus non-catalysed

Table of Contents

Catalytic cycles

Choosing a catalyst

25.3 Homogeneous catalysis: alkene (olefin) and alkyne metathesis

25.4 Homogeneous catalytic reduction of N2 to NH3

25.5 Homogeneous catalysis: industrial applicationsAlkene hydrogenation

Monsanto and Cativa acetic acid syntheses

TennesseeEastman acetic anhydride process

Hydroformylation (Oxo-process)

Alkene oligomerization

25.6 Homogeneous catalyst developmentPolymer-supported catalysts

Biphasic catalysis

25.7 Heterogeneous catalysis: surfaces and interactions with adsorbates

25.8 Heterogeneous catalysis: commercial applicationsAlkene polymerization: ZieglerNatta catalysis and metallocene catalysts

FischerTropsch carbon chain growth

HaberBosch process

Production of SO3 in the Contact process

Catalytic converters

Zeolites as catalysts for organic transformations: uses of ZSM-5

25.9 Heterogeneous catalysis: organometallic cluster models

26 d-Block metal complexes: reaction mechanisms26.1 Introduction

26.2 Ligand substitutions: some general pointsKinetically inert and labile complexes

Stoichiometric equations say nothing about mechanism

Types of substitution mechanism

Activation parameters

26.3 Substitution in square planar complexesRate equations, mechanism and the trans-effect

Ligand nucleophilicity

26.4 Substitution and racemization in octahedral complexesWater exchange

The EigenWilkins mechanism

Stereochemistry of substitution

Base-catalysed hydrolysis

Isomerization and racemization of octahedral complexes

26.5 Electron-transfer processesInner-sphere mechanism

Table of Contents

Outer-sphere mechanism

27 The f-block metals: lanthanoids and actinoids27.1 Introduction

27.2 f-Orbitals and oxidation states

27.3 Atom and ion sizesThe lanthanoid contraction

Coordination numbers

27.4 Spectroscopic and magnetic propertiesElectronic spectra and magnetic moments: lanthanoids

Luminescence of lanthanoid complexes

Electronic spectra and magnetic moments: actinoids

27.5 Sources of the lanthanoids and actinoidsOccurrence and separation of the lanthanoids

The actinoids

27.6 Lanthanoid metals

27.7 Inorganic compounds and coordination complexes of the lanthanoidsHalides

Hydroxides and oxides

Complexes of Ln(III)

27.8 Organometallic complexes of the lanthanoids�-Bonded complexes

Cyclopentadienyl complexes

Bis(arene) derivatives

Complexes containing the Z8-cyclooctatetraenyl ligand

27.9 The actinoid metals

27.10 Inorganic compounds and coordination complexes of thorium, uranium andplutonium

Thorium

Uranium

Plutonium

27.11 Organometallic complexes of thorium and uranium-Bonded complexes

Cyclopentadienyl derivatives

Complexes containing the Z8-cyclooctatetraenyl ligand

28 Inorganic materials and nanotechnology28.1 Introduction

28.2 Electrical conductivity in ionic solidsSodium and lithium ion conductors

d-Block metal(II) oxides

28.3 Transparent conducting oxides and their applications in devices

Table of Contents

Sn-doped In2O3 (ITO) and F-doped SnO2 (FTO)

Dye-sensitized solar cells (DSCs)

Solid state lighting: OLEDs

Solid state lighting: LECs

28.4 SuperconductivitySuperconductors: early examples and basic theory

High-temperature superconductors

Iron-based superconductors

Chevrel phases

Superconducting properties of MgB2

Applications of superconductors

28.5 Ceramic materials: colour pigmentsWhite pigments (opacifiers)

Adding colour

28.6 Chemical vapour deposition (CVD)High-purity silicon for semiconductors

a-Boron nitride

Silicon nitride and carbide

IIIV Semiconductors

Metal deposition

Ceramic coatings

Perovskites and cuprate superconductors

28.7 Inorganic fibresBoron fibres

Carbon fibres

Silicon carbide fibres

Alumina fibres

28.8 Graphene

28.9 Carbon nanotubes

29 The trace metals of life29.1 Introduction

Amino acids, peptides and proteins: some terminology

29.2 Metal storage and transport: Fe, Cu, Zn and VIron storage and transport

Metallothioneins: transporting some toxic metals

29.3 Dealing with O2Haemoglobin and myoglobin

Haemocyanin

Haemerythrin

Cytochromes P-450

29.4 Biological redox processes

Table of Contents

Blue copper proteins

The mitochondrial electron-transfer chain

Ironsulfur proteins

Cytochromes

29.5 The Zn2+ ion: Natures Lewis acidCarbonic anhydrase II

Carboxypeptidase A

Carboxypeptidase G2

Cobalt-for-zinc ion substitution

Appendices1 Greek letters with pronunciations

2 Abbreviations and symbols for quantities and units

3 Selected character tables

4 The electromagnetic spectrum

5 Naturally occurring isotopes and their abundances

6 Van der Waals, metallic, covalent and ionic radii

7 Pauling electronegativity values (�P) for selected elements of theperiodictable

8 Ground state electronic configurations of the elements andionization energies

9 Electron affinities

10 Standard enthalpies of atomization (aH) of the elements at 298 K

11 Selected standard reduction potentials (298 K)

12 Selected bond enthalpy terms

Answers to non-descriptive problems

Index

IUPAC: Brief Guide to the Nomenclature of Inorganic Chemistry

IBC

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CATHERINE E. HOUSECROFT & ALAN G. SHARPE INORGANIC ...

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