CHEM 4110: Advanced Inorganic Chemistry

by author

Read here Read at LibreTexts PDF

Publisher: Catherine McCusker
Subjects: Chemistry
Licence: CC BY-NC-SA, as LibreTexts states it. Non-commercial use only.
Who can read: Tweens profiles and older, judged from its title and subjects

LibreTexts writes equations in TeX, and here they show as TeX; the PDF has them typeset.

Front Matter
TitlePage
InfoPage
Table of Contents
Licensing
1: Introduction to Inorganic Chemistry
1.1: What is Inorganic Chemistry?
1.2: History of Inorganic Chemistry
1.3: Perspectives
1.4: Practice problems
2: Atomic Structure
2.1: Historical Development of Atomic Theory
2.1.1: The Periodic Table
2.1.2: Discovery of Subatomic Particles and the Bohr Atom
2.2: The Schrödinger Equation and Atomic Wavefunctions
2.3: Aufbau Principle
2.3.1: Shielding
2.3.2: The Aufbau Process
2.3.3: Electron Configuration of Transition Metals
2.4: Periodic Properties of Atoms
2.4.1: Ionization energy
2.4.2: Electron Affinity
2.4.3: Covalent and Ionic Radii
2.5: Problems
3: Simple Bonding Theories
3.1: Lewis Electron-Dot Diagrams
3.1.1: Formal Charge
3.1.2: Resonance
3.1.3: Breaking the Octet rule in Hypervalent Atoms
3.1.4: Breaking the Octet Rule in Hypovalent Atoms
3.2: The Shapes of Molecules (VSEPR Theory) and Orbital Hybridization
3.2.1: Multiple Bonds
3.2.2: Electronegativity and Atomic Size Effects
3.3: Bond Polarity and Bond Strength
3.4: Molecular Polarity
4: Symmetry and Group Theory
4.1: Symmetry Elements and Operations
4.2: Point Groups
4.2.1: Groups of Low and High Symmetry
4.2.2: Other Groups
4.3: Properties and Representations of Groups
4.3.1: Matrices
4.3.2: Representations of Point Groups
4.4: Character Tables
4.5: Examples and Applications of Symmetry
5: Molecular Orbitals
5.1: Formation of Molecular Orbitals from Atomic Orbitals
5.1.1: Molecular Orbitals from s Orbitals
5.1.2: Molecular Orbitals from p Orbitals
5.1.3: Molecular orbitals from d orbitals
5.1.4: Nonbonding Orbitals and Other Factors
5.2: Homonuclear Diatomic Molecules
5.2.1: Molecular Orbitals
5.2.2: Orbital Mixing
5.2.3: Diatomic Molecules of the First and Second Periods
5.2.4: Heteronuclear Diatomic Molecules
5.2.4.1: Orbital ionization energies
5.2.4.2: Polar bonds
5.3: Larger (Polyatomic) Molecules
5.3.1: Bifluoride anion
5.3.2: Carbon Dioxide
5.3.3: H₂O
5.3.4: NH₃
5.3.5: BF₃
5.4: BeH₂ is Linear and H₂O is Bent
5.5: Photoelectron Spectroscopy
5.6: Complexes with Multiple Metal-Metal Bonds
5.7: Problems
6: Coordination Chemistry - Structure and Isomers
6.1: Prelude to Coordination Chemistry I - Structure and Isomers
6.2: Nomenclature and Ligands
6.3: Isomerism
6.4: Coordination Numbers and Structures
6.5: Coordination Frameworks
6.6: Problems
7: Coordination Chemistry - Bonding
7.1: Evidence for Electronic Structures
7.2: Bonding Theories Overview
7.3: Crystal Field Theory
7.4: Ligand Field Theory
7.5: The Jahn-Teller Effect
7.6: Four- and Six-Coordinate Preferences
8: Coordination Chemistry - Spectroscopy
8.1: Absorption of Light
8.2: Types of Transition and Selection Rules for Transition Metal Complexes
8.3: Term States and Symbols for Multielectron Atoms
8.3.1: Finding Microstates and Term Symbols
8.3.2: Spin-Orbit Coupling
8.4: Ligand Field Transitions
8.5: Charge Transfer Transitions
8.5.1: Applications of Charge-Transfer
9: Coordination Chemistry - Reactions and Mechanisms
9.1: Thermodynamic Data
9.2: Introduction to Reactions of Metal Complexes
9.3: Substitutions Reactions
9.3.1: Introduction to Substitution Reactions
9.3.2: Inert and Labile Complexes
9.3.3: Mechanistic Possibilities
9.4: Kinetics Hint at the Reaction Mechanism
9.4.1: Rate Law for Dissociative Mechanisms
9.4.2: Rate Laws for Interchange Mechanisms
9.4.3: Rate Law for Associative Mechanisms
9.4.4: Preassociation Complexes
9.4.5: Activation Parameters
9.4.6: Some Reasons for Differing Mechanisms
9.5: Experimental Evidence in Octahedral Substitutions
9.5.1: Dissociation
9.5.2: Linear Free Energy Relationships
9.5.3: Associative Mechanisms
9.5.4: The conjugate base mechanism
9.5.5: The Kinetic Chelate Effect
9.6: Stereochemistry of Octahedral Reactions
9.6.1: Substitution in trans-en octahedral complexes
9.6.2: Substitution in cis-en octahedral complexes
9.6.3: Isomerization of Chelate Rings
9.7: Substitutions in Square Planar Complexes
9.7.1: Kinetics and Stereochemistry of Square Planar Reactions
9.7.2: Evidence for Associative Reactions
9.8: The Trans Effect
9.9: Redox Mechanisms
9.9.1: Inner Sphere Electron Transfer
9.9.2: Outer Sphere Electron Transfer
10: Organometallic Chemistry
10.1: Introduction to Organometallic Chemistry
10.2: Nomenclature, Ligands, and Classification
10.2.1: Survey of Organometallic Ligands
10.2.1.1: Carbon Monoxide (Carbonyl Complexes)
10.2.1.2: Ligands similar to CO
10.2.1.3: Hydrides and Dihydrogen Complexes
10.2.2: Bonding between Metal Atoms and Organic Pi Systems
10.2.2.1: Linear π Systems
10.2.2.2: Cyclic π systems
10.2.2.3: Odd-numbered π Systems
10.2.2.4: Fullerene Complexes
10.2.3: Metal-Carbon Bonds
10.2.3.1: Metal Alkyls
10.2.3.2: Carbenes
10.2.3.3: Carbyne (Alkylidyne) Complexes
10.2.3.4: Carbido and Cumulene Complexes
10.2.3.5: Carbon Wires- Polyyne and Polyene Bridges
10.3: Electron Counting in Organometallic Complexes
10.3.1: The 18 Electron Rule
10.3.2: Simplifying the Organometallic Complex by Deconstruction
10.4: Characterization of Organometallic Complexes
10.5: Organometallic Reactions and Catalysis
10.5.1: Reactions Involving Gain or Loss of Ligands
10.5.1.1: Ligand Dissociation and Substitution
10.5.1.2: Oxidative Addition
10.5.1.3: Reductive Elimination
10.5.1.4: Sigma Bond Metathasis
10.5.1.5: Application of Pincer Ligands
10.5.2: Reactions Invloving Modification of Unsaturated Ligands
10.5.2.1: Introduction to Insertion
10.5.2.2: CO Insertions (Alkyl Migration)
10.5.2.3: Migratory Insertion-1,2-Insertions
10.5.2.4: β-Elimination Reactions
10.5.2.5: Abstraction and Addition
10.6: Heterogeneous Catalysts
10.6.1: Ziegler-Natta Polymerizations
10.6.2: Water-Gas Shift Reaction
10.7: Organometallic Catalysts
10.7.1: Catalytic Deuteration
10.7.2: Hydroformylation
10.7.3: Monsanto Acetic Acid Process
10.7.4: Wacker (Smidt) Process
10.7.5: Hydrogenation by Wilkinson's Catalyst
10.7.6: Olefin Metathesis
10.8: Problems
10.8.1: Concept Review Questions Chapter 12
10.8.2: Homework Problems Chapter 12
11: Bioinorganic Chemistry
11.1: Biological Significance of Iron, Zinc, Copper, Molybdenum, Cobalt, Chromium, Vanadium, and Nickel
11.2: Introduction to Amino Acids and Proteins
11.3: Overview of Hemoglobin and Myoglobin
11.3.1: Myoglobin, Hemoglobin, and their Ligands
11.3.2: Oxygen Transport by the Proteins Myoglobin and Hemoglobin
11.4: Ferrodoxins, Hydrogenases, and Nitrogenases - Metal-Sulfide Proteins
11.4.1: Iron-sulfur Proteins and Models
11.4.2: Iron-sulfur Proteins and Models (Part 2)
11.4.3: Iron-sulfur Proteins and Models (Part 3)
11.4.4: Iron-sulfur Proteins and Models (Part 4)
11.5: The Reaction Pathways of Zinc Enzymes and Related Biological Catalysts
11.5.1: About Carbonic Anhydrase
11.5.2: Catalytic Mechanism
11.5.3: Metal Substitution
11.6: Metals in Medicine
11.6.1: Metal Deficiency and Disease
11.6.2: Toxic Effects of Metals
11.6.3: Aspects of Platinum Binding to DNA
11.6.4: Survey of Metals Used for Diagnosis and Chemotherapy
11.6.5: Platinum Anticancer Drugs- A Case Study
11.6.6: Mapping the Major Adducts of cis- and trans-DDP on DNA; Sequence Specificity
11.6.7: Structure of Platinum-DNA Complexes
11.6.8: Site-specifically Platinated DNA \(\;^{154}\)
11.6.9: Bioinorganic Chemistry of Platinum Anticancer Drugs- How Might They Work?
11.6.10: Bioinorganic Chemistry of Platinum Anticancer Drugs; How Might They Work? (Part 2)
11.6.11: Design of New Inorganic Anticancer Drugs
12: Applications- Photophysics and Photochemistry
12.1: Photophysical Processes
12.2: Photochemical Processes
12.2.1: Dexter Energy Transfer
12.2.2: Fluorescence Resonance Energy Transfer
12.3: Laser Fundamentals
12.4: Atmospheric Photochemistry- Ozone
12.5: Applications of Photochemistry- Photoredox Catalysis
13: Applications - Nanomaterials
13.1: Prelude to Basic Science of Nanomaterials
13.2: Physics and Length Scales- Cavity Laser, Coulomb Blockade, Nanoscale Magnets
13.3: Semiconductor Quantum Dots
13.4: Synthesis of Semiconductor Nanocrystals
13.5: Surface Energy
13.6: Nanoscale Metal Particles
13.7: Applications of Nanomaterials
13.8: Discussion Questions
13.9: Problems
13.10: References
14: Appendix
14.1: Advanced Group Theory
14.1.1: The Exploitation of Symmetry Can Help Simplify Numerical Calculations
14.1.2: Symmetry Elements and Operations Define the Point Groups
14.1.3: Symmetry Operations Define Groups
14.1.4: Symmetry Operations as Matrices
14.1.5: Molecules can be Represented by Reducible Representations
14.1.6: Character Tables Summarize the Properties of a Point Group
14.1.7: Characters of Irreducible Representations
14.1.8: Using Symmetry to Solve Secular Determinants
14.1.9: Generating Operators
14.1.10: Molecular Motions of a Molecule can be Represented by a Reducible Reperesentation
14.1.11: Reducible Representations are Comprised of Irreducible Representations
14.1.12: Normal Modes of Vibrations Describe how Molecules Vibrate
14.1.13: Symmetry of Vibrations Describes their Spectroscopic Behavior
14.1.14: Symmetry Adapted Linear Combinations are the Sum over all Basis functions
14.1.15: Molecular Orbitals can be Constructed on the Basis of Symmetry
14.1.E: Group Theory - The Exploitation of Symmetry (Exercises)
14.1.T: Character Tables
14.1.T: Correlation Tables
14.2: Derivation of Laporte Rule
14.3: Periodic Table
14.4: Character Tables
14.5: Tanabe-Sugano Diagrams
Back Matter
Index
Glossary
Detailed Licensing
Detailed Licensing

CHEM 4110: Advanced Inorganic Chemistry

Contents