CHM 321: Inorganic Chemistry

by Bryan P. Nell

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This is the LibreText Open Educational Resource (OER) book for the CHM 321: Inorganic Chemistry course at Ripon College.

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Publisher
Ripon College
Subjects
Chemistry
Licence
CC BY-NC-SA 4.0, as LibreTexts states it. Non-commercial use only.
Who can read
Tweens profiles and older, judged from its title and subjects

Contents

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  1. Front Matter
  2. TitlePage
  3. InfoPage
  4. Table of Contents
  5. Licensing
  6. 1: Atomic Structure, Molecular Structure, and Bonding
  7. 1.1: Introduction to Inorganic Chemistry
  8. 1.1.1: What is Inorganic Chemistry?
  9. 1.1.2: Inorganic vs Organic Chemistry
  10. 1.1.3: History of Inorganic Chemistry
  11. 1.2: Atomic Structure
  12. 1.2.1: Historical Development of Atomic Theory
  13. 1.2.1.1: The Periodic Table
  14. 1.2.1.2: Discovery of Subatomic Particles and the Bohr Atom
  15. 1.2.2: The Schrödinger equation, particle in a box, and atomic wavefunctions
  16. 1.2.2.1: Particle in a Box
  17. 1.2.2.2: Quantum Numbers and Atomic Wave Functions
  18. 1.2.2.3: Aufbau Principle
  19. 1.2.2.4: Shielding
  20. 1.2.3: Periodic Properties of Atoms
  21. 1.2.3.1: Ionization energy
  22. 1.2.3.2: Electron Affinity
  23. 1.2.3.3: Covalent and Ionic Radii
  24. 1.3: Rutherford's Atom
  25. 1.4: Bohr's Atom
  26. 1.5: Simple Bonding Theory
  27. 1.5.1: Lewis Electron-Dot Diagrams
  28. 1.5.1.1: Resonance
  29. 1.5.1.2: Breaking the octet rule with higher electron counts (hypervalent atoms)
  30. 1.5.1.3: Formal Charge
  31. 1.5.1.4: Lewis fails to predict unusual cases- Boron and Beryllium
  32. 1.5.2: Valence Shell Electron-Pair Repulsion
  33. 1.5.2.1: Lone Pair Repulsion
  34. 1.5.2.2: Multiple Bonds
  35. 1.5.2.3: Electronegativity and Atomic Size Effects
  36. 1.5.3: Molecular Polarity
  37. 1.5.4: Hydrogen Bonding
  38. 1.5.5: Valence Bond Theory
  39. 1.5.6: Hybrid Atomic Orbitals
  40. 1.6: Molecular Orbital Theory
  41. 1.6.1: Prelude to Molecular Orbital Theory
  42. 1.6.2: Formation of Molecular Orbitals from Atomic Orbitals
  43. 1.6.2.1: Molecular Orbitals from s Orbitals
  44. 1.6.2.2: Molecular Orbitals from p Orbitals
  45. 1.6.2.3: Molecular orbitals from d orbitals
  46. 1.6.2.4: Nonbonding Orbitals and Other Factors
  47. 1.6.3: Homonuclear Diatomic Molecules
  48. 1.6.3.1: Molecular Orbitals
  49. 1.6.3.2: Orbital Mixing
  50. 1.6.3.3: Diatomic Molecules of the First and Second Periods
  51. 1.6.3.4: Photoelectron Spectroscopy
  52. 1.6.4: Heteronuclear Diatomic Molecules
  53. 1.6.4.1: Polar bonds
  54. 1.6.4.2: Ionic Compounds and Molecular Orbitals
  55. 2: Molecular Symmetry and Group Theory
  56. 2.1: Symmetry Elements and Operations
  57. 2.2: Point Groups
  58. 2.2.1: Groups of Low and High Symmetry
  59. 2.2.2: Other Groups
  60. 2.3: Properties and Representations of Groups
  61. 2.3.1: Matrices
  62. 2.3.2: Representations of Point Groups
  63. 2.3.3: Character Tables
  64. 2.4: Examples and Applications of Symmetry
  65. 2.4.1: Molecular Vibrations
  66. 2.4.2: Chirality
  67. 2.5: Generating SALCs for Polyatomic Molecules
  68. 2.5.1: Bifluoride anion
  69. 2.5.2: Carbon Dioxide
  70. 2.5.3: H₂O
  71. 2.5.4: NH₃
  72. 2.5.5: CO₂ (Revisted with Projection Operators)
  73. 2.5.6: BF₃
  74. 3: Acid-Base Chemistry and an Introduction to Coordination Compounds
  75. 3.1: Bronsted-Lowry acids and bases
  76. 3.2: Lewis Acids and Bases
  77. 3.3: Acidity of the Hexaaqua Ions
  78. 3.4: Hard/Soft Acids and Bases
  79. 3.5: Quantitative Measures of Hardness and Softness
  80. 3.6: Coordination Chemistry- Structure and Isomers
  81. 3.6.1: History
  82. 3.6.2: Nomenclature and Ligands
  83. 3.6.3: Acid-Base and Donor-Acceptor Chemistry
  84. 3.6.3.1: Acid-Base Models as Organizing Concepts
  85. 3.6.3.2: Lewis Concept and Frontier Orbitals
  86. 3.6.3.3: Hard and Soft Acids and Bases
  87. 3.6.3.4: Problems
  88. 3.6.4: Coordination Numbers and Structures
  89. 3.6.5: Isomerism
  90. 3.7: Coordination Chemistry- Bonding
  91. 3.7.1: Crystal Field Theory
  92. 3.7.2: Crystal Field Stabilization Energy
  93. 3.7.3: Factors That Affect Crystal Field Splitting
  94. 3.7.4: Ligand Field Theory
  95. 3.7.5: Metal-Metal Bonds
  96. 3.7.5.1: Metal-Metal Multiple Bonds
  97. 3.7.6: Jahn-Teller Distortions
  98. 4: Electronic Structure and Spectra of d-Metal Complexes
  99. 4.1: Absorption of Light
  100. 4.1.1: Beer-Lambert Absorption Law
  101. 4.2: Quantum Numbers of Multielectron Atoms
  102. 4.2.1: Finding Microstates and Term Symbols
  103. 4.2.2: Spin-Orbit Coupling
  104. 4.3: Electronic Spectra of Coordination Compounds
  105. 4.3.1: Symmetry labels for split terms
  106. 4.3.2: Correlation Diagrams
  107. 4.3.3: Tanabe-Sugano Diagrams
  108. 4.3.4: Applications of Tanabe-Sugano Diagrams
  109. 4.3.5: Tetrahedral Complexes
  110. 4.3.6: Selection Rules
  111. 4.3.7: Charge-Transfer Spectra
  112. 4.3.8: Applications of Charge-Transfer
  113. 5: Reactions of d-Metal Complexes
  114. 5.1: Thermodynamic Stability of Metal Complexes
  115. 5.2: Trends in Kinetic Lability
  116. 5.3: Ligand Substitution Mechanisms
  117. 5.4: Substitutions in Square Planar Complexes
  118. 5.4.1: Kinetics and Stereochemistry of Square Planar Reactions
  119. 5.4.2: Evidence for Associative Reactions
  120. 5.5: The Trans Effect Observation
  121. 5.6: The Trans Effect Explanation
  122. 5.7: Redox Mechanisms
  123. 5.7.1: Outer Sphere Electron Transfer
  124. 5.7.2: Inner Sphere Electron Transfer
  125. 6: Organometallic Chemistry
  126. 6.1: Introduction to Organometallic Chemistry
  127. 6.2: Nomenclature, Ligands, and Classification
  128. 6.3: Electron Counting in Organometallic Complexes
  129. 6.3.1: The 18 Electron Rule
  130. 6.3.2: Simplifying the Organometallic Complex by Deconstruction
  131. 6.4: Survey of Organometallic Ligands
  132. 6.4.1: Carbon Monoxide (Carbonyl Complexes)
  133. 6.4.2: Ligands similar to CO
  134. 6.4.3: Hydrides and Dihydrogen Complexes
  135. 6.5: Bonding between Metal Atoms and Organic Pi Systems
  136. 6.5.1: Linear π Systems
  137. 6.5.2: Cyclic π systems
  138. 6.5.3: Odd-numbered π Systems
  139. 6.5.4: Fullerene Complexes
  140. 6.6: Metal-Carbon Bonds
  141. 6.6.1: Metal Alkyls
  142. 6.6.2: Carbenes
  143. 6.6.3: Carbyne (Alkylidyne) Complexes
  144. 6.6.4: Carbido and Cumulene Complexes
  145. 6.6.5: Carbon Wires- Polyyne and Polyene Bridges
  146. 6.7: Characterization of Organometallic Complexes
  147. 7: Organometallic Reactions and Catalysis
  148. 7.1: Reactions Involving Gain or Loss of Ligands
  149. 7.1.1: Ligand Dissociation and Substitution
  150. 7.1.2: Oxidative Addition
  151. 7.1.3: Reductive Elimination
  152. 7.1.4: Sigma Bond Metathasis
  153. 7.1.5: Application of Pincer Ligands
  154. 7.2: Reactions Invloving Modification of Unsaturated Ligands
  155. 7.2.1: Introduction to Insertion
  156. 7.2.2: CO Insertions (Alkyl Migration)
  157. 7.2.3: Migratory Insertion-1,2-Insertions
  158. 7.2.4: β-Elimination Reactions
  159. 7.2.5: Abstraction and Addition
  160. 7.3: Organometallic Catalysts
  161. 7.3.1: Catalytic Deuteration
  162. 7.3.2: Hydroformylation
  163. 7.3.3: Monsanto Acetic Acid Process
  164. 7.3.4: Wacker (Smidt) Process
  165. 7.3.5: Hydrogenation by Wilkinson's Catalyst
  166. 7.3.6: Olefin Metathesis
  167. 7.4: Heterogeneous Catalysts
  168. 7.4.1: Ziegler-Natta Polymerizations
  169. 7.4.2: Water-Gas Shift Reaction
  170. 7.5: Problems
  171. 7.5.1: Concept Review Questions Chapter 12
  172. 7.5.2: Homework Problems Chapter 12
  173. 8: Solid State Chemistry
  174. 8.1: Prelude to Metals and Alloys
  175. 8.2: Unit Cells and Crystal Structures
  176. 8.3: Crystal Structures of Metals
  177. 8.4: Conduction in Metals
  178. 8.5: Atomic Orbitals and Magnetism
  179. 8.6: Ferro-, Ferri- and Antiferromagnetism
  180. 8.7: Hard and Soft Magnets
  181. 8.8: Defects in Metallic Crystals
  182. 8.9: X-ray Crystallography
  183. 8.10: Miller Indices (hkl)
  184. 8.11: Powder X-ray Diffraction
  185. 8.12: Prelude to Ionic and Covalent Solids - Structures
  186. 8.13: Close-packing and Interstitial Sites
  187. 8.14: Structures Related to NaCl and NiAs
  188. 8.15: Tetrahedral Structures
  189. 8.16: Layered Structures and Intercalation Reactions
  190. 8.17: Ionic Radii and Radius Ratios
  191. 8.18: Structure Maps
  192. 8.19: Energetics of Crystalline Solids- The Ionic Model
  193. 8.20: Born-Haber Cycles for NaCl and Silver Halides
  194. 8.21: Lattice Energies and Solubility
  195. 8.22: Spinel, Perovskite, and Rutile Structures
  196. 8.23: Kapustinskii Equation
  197. 8.24: New Page
  198. 9: Bioinorganic Chemistry
  199. 9.1: Biological Significance of Iron, Zinc, Copper, Molybdenum, Cobalt, Chromium, Vanadium, and Nickel
  200. 9.2: Introduction to Amino Acids and Proteins
  201. 9.3: Overview of Hemoglobin and Myoglobin
  202. 9.3.1: Myoglobin, Hemoglobin, and their Ligands
  203. 9.3.2: Oxygen Transport by the Proteins Myoglobin and Hemoglobin
  204. 9.4: Ferrodoxins, Hydrogenases, and Nitrogenases - Metal-Sulfide Proteins
  205. 9.4.1: Iron-sulfur Proteins and Models
  206. 9.4.2: Iron-sulfur Proteins and Models (Part 2)
  207. 9.4.3: Iron-sulfur Proteins and Models (Part 3)
  208. 9.4.4: Iron-sulfur Proteins and Models (Part 4)
  209. 9.5: The Reaction Pathways of Zinc Enzymes and Related Biological Catalysts
  210. 9.5.1: About Carbonic Anhydrase
  211. 9.5.2: Catalytic Mechanism
  212. 9.5.3: Metal Substitution
  213. 9.6: Metals in Medicine
  214. 9.6.1: Metal Deficiency and Disease
  215. 9.6.2: Toxic Effects of Metals
  216. 9.6.3: Aspects of Platinum Binding to DNA
  217. 9.6.4: Survey of Metals Used for Diagnosis and Chemotherapy
  218. 9.6.5: Platinum Anticancer Drugs- A Case Study
  219. 9.6.6: Mapping the Major Adducts of cis- and trans-DDP on DNA; Sequence Specificity
  220. 9.6.7: Structure of Platinum-DNA Complexes
  221. 9.6.8: Site-specifically Platinated DNA \(\;^{154}\)
  222. 9.6.9: Bioinorganic Chemistry of Platinum Anticancer Drugs- How Might They Work?
  223. 9.6.10: Bioinorganic Chemistry of Platinum Anticancer Drugs; How Might They Work? (Part 2)
  224. 9.6.11: Design of New Inorganic Anticancer Drugs
  225. 9.7: Electron Transfer
  226. 10: Special Topics
  227. 10.1: f-Block Metals- Lanthanides and Actinides
  228. 10.1.1: Introduction
  229. 10.1.2: f-Orbitals and Oxidation States
  230. 10.1.3: Atoms and Ion Sizes
  231. 10.1.3A: The Lanthanoid Contraction
  232. 10.1.3B: Coordination Numbers
  233. 10.1.4: Spectroscopic and Magnetic Properties
  234. 10.1.4A: Electronic Spectra and Magnetic Moments - Lanthanoids
  235. 10.1.4B: Luminescence of Lanthanoid Complexes
  236. 10.1.4C: Electronic Spectra and Magnetic Moments - Actinoids
  237. 10.1.5: Sources of the Lanthanoids and Actinoids
  238. 10.1.5A: Occurrence and Separation of the Lanthanoids
  239. 10.1.5B: The Actinoids
  240. 10.1.6: Lanthanoid Metals
  241. 10.1.7: Inorganic Compounds and Coordination Complexes of the Lanthanoids
  242. 10.1.7A: Halides
  243. 10.1.7B: Hydroxides and Oxides
  244. 10.1.7C: Complexes of Ln(III)
  245. 10.1.8: Organometallic Complexes of the Lanthanoids
  246. 10.1.8A: \(\sigma\)-Bonded Complexes
  247. 10.1.8B: Cyclopentadienyl Complexes
  248. 10.1.8C: Bis(arene) Derivatives
  249. 10.1.8D: Complexes Containing the \(\eta^8\)-cyclooctatetraenyl Ligand
  250. 10.1.9: The Actinoid Metals
  251. 10.1.10: Inorganic Compounds and Coordination Complexes of Thorium, Uranium, and Plutonium
  252. 10.1.10A: Thorium
  253. 10.1.10B: Uranium
  254. 10.1.10C: Plutonium
  255. 10.1.11: Organometallic Complexes of Thorium and Uranium
  256. 10.1.11A: (\sigma\)-Bonded Complexes
  257. 10.1.11B: Cyclopentadienyl Derivatives
  258. 10.1.11C: Complexes Containing the \(\eta^8\)-cyclooctatetraenyl Ligand
  259. 10.2: Physical Inorganic Techniques
  260. 10.2.1: Electronic Spectroscopy
  261. 10.2.1A: UV-VIS Absorption Spectroscopy
  262. 10.2.1B: Types of Absorption
  263. 10.2.1C: Absorbance and the Beer-Lambert Law
  264. 10.2.1D: Emission Spectroscopy
  265. 10.2.2: Nuclear Magnetic Resonance (NMR) Spectroscopy
  266. 10.2.3: Electron Paramagnetic Resonance (EPR) Spectroscopy
  267. 10.2.3A: What is EPR Spectroscopy?
  268. 10.2.3B: The Zeeman Electronic Effect
  269. 10.2.3C: EPR Spectra
  270. 10.2.4: Mossbauer Spectroscopy
  271. 10.2.4A: The Technique of Mossbauer Spectroscopy
  272. 10.2.4B: What Can Isomer Shift Data Tell Us?
  273. 10.2.5: Structure Determination - Diffraction Methods
  274. 10.2.5A: X-Ray Diffraction (XRD)
  275. 10.2.5B: Single Crystal X-Ray Diffraction
  276. 10.2.5C: Powder X-Ray Diffraction
  277. 10.2.5D: Single Crystal Neutron Diffraction
  278. 10.2.5E: Electron Diffraction
  279. 10.2.5F: Low-Energy Electron Diffraction (LEED)
  280. 10.2.5G: Structural Databases
  281. 10.2.6: Photoelectron Spectroscopy (PES, UPS, XPS, ESCA)
  282. 10.2.7: Mass Spectrometry
  283. 10.2.7A: Electron Ionization (EI)
  284. 10.2.7B: Fast Atom Bombardment (FAB)
  285. 10.2.7C: Matrix-Assisted Laser Desorption Ionization Time-of-Flight (MALDI-TOF)
  286. 10.2.7D: Electrospray Ionization (ESI)
  287. 10.3: Fluxional Behavior
  288. 10.3.1: Determination of Energetics of Fluxional Molecules by NMR
  289. Back Matter
  290. Index
  291. Glossary
  292. Detailed Licensing
  293. Detailed Licensing