Inorganic Chemistry: Principles and Properties

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Half Title
Inorganic Chemistry: Principles and Properties
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Dedication
Preface
Contents
Preface
1. Lewis Structure and Valence Shell Electron Pair Repulsion
	1.1 Lewis structure
	1.2 Valence shell electron pair repulsion
		(a) Application of VSEPR model to some real molecules
		(b) Trigonal bipyramidal molecules
		(c) Summary of VSEPR method: molecular geometry/shape
		(d) Some significant limitations of the VSEPR model
	1.3 Hybridization
		(a) Bent’s Rule
		(b) Berry pseudorotation
		(c) Bonding involving pπ-pπ and dπ-pπ interactions
		(d) Multi-center bond models
		(e) Exceptions to the VSEPR rules and possible effects of ligand-ligand repulsions
	Further reading
	Exercises
2. Molecular Symmetry
	2.1 Symmetry, point groups, and character tables
		(a) Symmetry operations and symmetry elements
		(b) Protocol for determining molecular point grou
		(c) Character tables
	2.2 Orbital symmetries
		Orbital degeneracy inoctahedral symmetry
	Further reading
	Exercises
3. Molecular Orbital Theory
	3.1 LCAO-MO theory
		(a) Basic rules of MO theory
		(b) The overlap criterion of bonding
		(c) Examples of MO approach to diatomic molecules
		(i) Homonuclear diatomic molecules
		(ii) Heteronuclear diatomic molecule
	3.2 The electronic structure by MO theory
		(i) Diatomic molecule: AB type (HF; linear, C∞v)
		(ii) Triatomic molecule: AB2 type, σ bonding (BeH2; linear, D∞h)
		(iii) Triatomic molecule: AB2 type, σ and π bonding (CO2; linear, D∞h)
		(iv) Triatomic molecule: AB2E2 type (H2O; V-shape/bent, C2v)
		(v) Tetratomic molecule: AB3 type, σ bonding (BH3; equilateral triangular planar, D3h)
		(vi) Tetratomic molecule: AB3 type, σ and π bonding (BF3; triangular planar, D3h)
		(vii) Tetratomic molecule: AB3E1 type (NH3; pyramidal, C3v)
		(viii) Pentatomic molecule: AB4 type (CH4; tetrahedral, Td)
		(ix) Pentatomic molecule: AB4E2 type (XeF4; square planar, D4h)
		(x) Hexatomic molecule: AB5 type (BrF5, ML5 (see Chapter 6); square pyramidal, C4v)
	3.3 Three-center bonding: Electron-deficient compound B2H6
	Further reading
	Exercises
4. Redox Reactions
	4.1 Redox half-cell reactions
	4.2 Equilibrium constant and redox potential
	4.3 Stability field of water
	4.4 Calculation of cell potential and equilibrium constant
	4.5 Inner-sphere electron transfer concepts through electrochemical studies
	4.6 Proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT)
		(a) Effect of pH on the reduction potentials: quinone/hydroquinone redox couple
		(b) Ru-bpy/py system
		(c) Ferrocenecarboxylic acid
		(d) Thermodynamic justification for hydrogen atom abstraction
	Further reading
	Exercises
5. Spectroscopic Terms and Spin-Orbit Coupling
	5.1 L-S and j- j coupling
	5.2 Term symbols
	5.3 Spin-orbit interaction
	Further reading
	Exercises
6. Chemistry of d-Block Elements
	Bonding theories
	6.1 Valence bond theory
	6.2 Crystal field theory
		(a) Crystal field splitting diagrams for octahedral and tetrahedral geometry
		(b) Strength of the ligands
		(c) Spectrochemical series
		(d) Octahedral (high spin and low spin) and tetrahedral complexes, and CFSE
		(e) Consequences of d-orbital splitting
		i) Ionic radii
		ii) Lattice enthalpy
		iii) Hydration enthalpy
		iv) Spinel structures
		v) The Irving-Williams series (Stability constants)
		(f) Tetragonal distortion and Jahn-Teller distortion
		(g) Crystal field splitting diagram for square planar symmetry
		(h) Crystal field splitting diagrams for trigonal bipyramidal and square pyramidal symmetry
	6.3 Splitting of levels and terms
		(i) Crystal field splitting of Russell-Saunders terms in octahedral symmetry
		(ii) Simplifying rules to construct CF diagrams
	6.4 Magnetic properties
		(a) Orbital contribution to magnetic moment
		(b) Spectroscopic term symbols and orbital contribution
		(c) Forms of paramagnetism
		(d) Magnetic field dependence
		(e) Super-exchange phenomena
		(f) Temperature-independent paramagnetism (TIP)
		(g) Spin-crossover complexes
	6.5 Nephelauxetic effect
	6.6 Deficiencies of crystal field theory
	6.7 Electronic spectral properties
		a) Orgel diagrams for octahedral and tetrahedral symmetry
		b) Tanabe-Sugano diagrams
		c) Charge transfer transitions
	6.8 Molecular orbital treatment (theory)
		(a) ML6 complexes (say, M = Cr0, L = CO).
			M–L σ -Bonding
			M–L π-bonding and effects of π bonding
		(b) ML4 complex (square planar geometry)
	6.9 Metal-metal bonding
	Further reading
	Exercises
7. Reactions of d-Block Complexes
	7.1 Labile and inert metal ions
	7.2 Ligand substitution reactions
		(1) Octahedral complexes
		(a) Anation of Co(III) complexes (leaving group constant)
		(b) Substitution of Ru(III) complexes
		(c) Aquation of Co(III) complexes (leaving group varied):
		(2) Planar complexes
		The trans effect
	7.3 Electron transfer (redox) reactions
		(a) Inner-sphere (atom transfer) reactions
		(b) Outer-sphere reactions
		• Electron self-exchange
		• Cross transfer
	Further reading
	Exercises
8. Organometallic Chemistry of d-Block Elements
	8.1 Types of ligand
	8.2 Metal-carbonyl bonding
	8.3 Metal-olefin bonding
	8.4 Counting of valence electrons (18-electron rule)
	8.5 Organometallic reactions: oxidative addition, reductive elimination, insertion (migratory insertion), and β -hydrogen (β -hydride) elimination
		Oxidative addition
		Reductive elimination
		Insertion (or migratory insertion)
		β -Hydrogen (β -hydride) elimination
	8.6 Noninnocent ligands in organometallic chemistry
		Ligand redox-based oxidative addition and reductive elimination
	8.7 The σ complexes
	8.8 Bis(cyclopentadienyl)M(II) complexes
	Further reading
	Exercises
9. Organometallic Catalysis
	9.1 Why 4d metal ions?
	9.2 Hydrogenation of alkene
	9.3 Hydroformylation reaction (oxo process)
	9.4 Oxidation of alkenes (Wacker process)
	9.5 Olefin hydrocyanation
	9.6 Homogeneous/heterogeneous catalysis: Propylene polymerization
	Further reading
	Exercises
10. Bioinorganic Chemistry
	10.1 Role of metal ions
	10.2 The importance of iron
		(a) Iron-transport protein: transferrin
		(b) Iron-storage protein: ferretin
	10.3 Dioxygen and hemeproteins
		(a) Hemoglobin and myoglobin
		The Bohr effect, CO2 transport
		(b) Heme enzymes
	10.4 Aerobic metabolism
	10.5 Nonheme iron proteins/enzymes
		Hemerythrin, ribonucleotide reductase, and methane monoxygenase
	10.6 Nickel enzyme, urease
	10.7 Copper proteins
		Superoxide dismutase
		Galactose oxidase
		Hemocyanin, tyrosinase, and catechol oxidase
	10.8 Zinc enzymes
	10.9 Photosynthesis
	10.10 Nitrogenase
	Further reading
	Exercises
Answers to Exercises
	Chapter 1
	Chapter 2
	Chapter 3
	Chapter 4
	Chapter 5
	Chapter 6
	Chapter 7
	Chapter 8
	Chapter 9
	Chapter 10
Index