Inorganic Chemistry

by Haas et al.

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Duke University
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Chemistry, Inorganic Chemistry
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CC BY 4.0, as LibreTexts states it
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Contents

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  1. Front Matter
  2. TitlePage
  3. InfoPage
  4. Table of Contents
  5. Licensing
  6. 1: Introduction to Inorganic Chemistry
  7. 1.1: What is Inorganic Chemistry?
  8. 1.2: Inorganic vs Organic Chemistry
  9. 1.3: History of Inorganic Chemistry
  10. 1.4: Perspectives
  11. 1.5: Practice problems
  12. 2: Atomic Structure
  13. 2.1: Historical Development of Atomic Theory
  14. 2.1.1: The Periodic Table
  15. 2.1.2: Discovery of Subatomic Particles and the Bohr Atom
  16. 2.2: The Schrödinger equation, particle in a box, and atomic wavefunctions
  17. 2.2.1: Particle in a Box
  18. 2.2.2: Quantum Numbers and Atomic Wave Functions
  19. 2.2.3: Aufbau Principle
  20. 2.2.4: Shielding
  21. 2.3: Periodic Properties of Atoms
  22. 2.3.1: Ionization energy
  23. 2.3.2: Electron Affinity
  24. 2.3.3: Covalent and Ionic Radii
  25. 2.4: Problems
  26. 3: Simple Bonding Theory
  27. 3.1: Lewis Electron-Dot Diagrams
  28. 3.1.1: Resonance
  29. 3.1.2: Breaking the octet rule with higher electron counts (hypervalent atoms)
  30. 3.1.3: Formal Charge
  31. 3.1.4: Lewis Fails to Predict Unusual Cases - Boron and Beryllium
  32. 3.2: Valence Shell Electron-Pair Repulsion
  33. 3.2.1: Lone Pair Repulsion
  34. 3.2.2: Multiple Bonds
  35. 3.2.3: Electronegativity and Atomic Size Effects
  36. 3.2.4: Ligand Close Packing
  37. 3.3: Molecular Polarity
  38. 3.4: Hydrogen Bonding
  39. 4: Symmetry and Group Theory
  40. 4.1: Symmetry Elements and Operations
  41. 4.2: Point Groups
  42. 4.2.1: Groups of Low and High Symmetry
  43. 4.2.2: Other Groups
  44. 4.3: Properties and Representations of Groups
  45. 4.3.1: Matrices
  46. 4.3.2: Representations of Point Groups
  47. 4.3.3: Character Tables
  48. 4.4: Examples and Applications of Symmetry
  49. 4.4.1: Chirality
  50. 4.4.2: Molecular Vibrations
  51. 4.P: Problems (under construction)
  52. 5: Molecular Orbitals
  53. 5.1: Formation of Molecular Orbitals from Atomic Orbitals
  54. 5.1.1: Molecular Orbitals from s Orbitals
  55. 5.1.2: Molecular Orbitals from p Orbitals
  56. 5.1.3: Molecular orbitals from d orbitals
  57. 5.1.4: Nonbonding Orbitals and Other Factors
  58. 5.2: Homonuclear Diatomic Molecules
  59. 5.2.1: Molecular Orbitals
  60. 5.2.2: Orbital Mixing
  61. 5.2.3: Diatomic Molecules of the First and Second Periods
  62. 5.2.4: Photoelectron Spectroscopy
  63. 5.3: Heteronuclear Diatomic Molecules
  64. 5.3.1: Orbital ionization energies
  65. 5.3.2: Polar bonds
  66. 5.3.3: Ionic Compounds and Molecular Orbitals
  67. 5.4: Larger (Polyatomic) Molecules
  68. 5.4.1: Bifluoride anion
  69. 5.4.2: Carbon Dioxide
  70. 5.4.3: H₂O
  71. 5.4.4: NH₃
  72. 5.4.5: CO₂ (Revisted with Projection Operators)
  73. 5.4.6: BF₃
  74. 5.P: Problems
  75. 6: Acid-Base and Donor-Acceptor Chemistry
  76. 6.1: Acid-Base Models as Organizing Concepts
  77. 6.2: Arrhenius Concept
  78. 6.3: Brønsted-Lowry Concept
  79. 6.3.1: Brønsted-Lowry Concept
  80. 6.3.2: Rules of Thumb for thinking about the relationship between Molecular Structure and Brønsted Acidity and Basicity*
  81. 6.3.3: The acid-base behavior of binary element hydrides is determined primarily by the element's electronegativity and secondarily by the element-hydrogen bond strength
  82. 6.3.4: Brønsted-Lowry Superacids and the Hammett Acidity Function
  83. 6.3.5: Thermodynamics of Solution-Phase Brønsted Acidity and Basicity
  84. 6.3.6: Thermodynamics of Gas Phase Brønsted Acidity and Basicity
  85. 6.3.7: The Acidity of an Oxoacid is Determined by the Electronegativity and Oxidation State of the Oxoacid's Central Atom*
  86. 6.3.8: High Charge-to-Size Ratio Metal Ions Act as Brønsted Acids in Water
  87. 6.3.9: The Solvent System Acid Base Concept
  88. 6.3.10: Acid-Base Chemistry in Amphoteric Solvents and the Solvent Leveling Effect
  89. 6.3.11: Non-nucleophilic Brønsted-Lowry Superbases
  90. 6.4: Lewis Concept and Frontier Orbitals
  91. 6.4.1: The frontier orbital approach considers Lewis acid-base reactions in terms of the donation of electrons from the base's highest occupied orbital into the acid's lowest unoccupied orbital.
  92. 6.4.2: All other things being equal, electron withdrawing groups tend to make Lewis acids stronger and bases weaker while electron donating groups tend to make Lewis bases stronger and acids weaker
  93. 6.4.3: The electronic spectra of charge transfer complexes illustrate the impact of frontier orbital interactions on the electronic structure of Lewis acid-base adducts
  94. 6.4.4: Substances' solution phase Lewis basicity towards a given acid may be estimated using the enthalphy change for dissociation of its adduct with a reference acid of similar hardness.
  95. 6.4.5: In the boron trifluoride affinity scale, the enthalphy change on formation of an adduct between the base and boron trifluoride is taken as a measure of Lewis basicity.
  96. 6.4.6: Lewis base strength may also be estimated by measuring structural or energy changes upon formation of a Lewis acid-base complex, as illustrated by efforts to spectroscopically assess the strengths of halogen bonds
  97. 6.4.7: Bulky groups weaken the strength of Lewis acids and bases because they introduce steric strain into the resulting acid-base adduct.
  98. 6.4.8: Frustrated Lewis pair chemistry uses Lewis acid and base sites within a molecule that are sterically restricted from forming an adduct with each other.
  99. 6.5: Intermolecular Forces
  100. 6.5.1: Host-Guest Chemistry and π-π Stacking Interactions
  101. 6.5.2: Hydrogen bonds may be considered as a special type of Lewis acid-base interaction in which a Lewis acid hydrogen ion is shared between Lewis bases
  102. 6.6: Hard and Soft Acids and Bases
  103. 6.6.1: Quantitative Measures of Hardness, Softness, and Acid-Base Interactions from a Hard Soft Acid-Base Principle Perspective Involve Orbital Energies and/or Apportioning Acid-Base Bonding in Terms of Electrostatic and Covalent Factors
  104. 6.6.2: Hard-Hard and Soft-Soft preferences may be explained and quantified in terms of electrostatic and covalent and electronic stabilization on the stability of Lewis acid-base adducts
  105. 7: The Crystalline Solid State
  106. 7.1: Molecular Orbitals and Band Structure
  107. 7.1.1: Prelude to Electronic Properties of Materials - Superconductors and Semiconductors
  108. 7.1.2: Metal-Insulator Transitions
  109. 7.1.3: Periodic Trends- Metals, Semiconductors, and Insulators
  110. 7.1.4: Semiconductors- Band Gaps, Colors, Conductivity and Doping
  111. 7.1.5: Semiconductor p-n Junctions
  112. 7.1.6: Diodes, LEDs and Solar Cells
  113. 7.1.7: Amorphous Semiconductors
  114. 7.1.8: Discussion Questions
  115. 7.1.9: Problems
  116. 7.1.10: References
  117. 7.2: Formulas and Structures of Solids
  118. 7.2.1: The Solid State of Matter
  119. 7.2.2: Lattice Structures in Crystalline Solids
  120. 7.3: Superconductivity
  121. 7.3.1: Superconductors
  122. 7.4: Bonding in Ionic Crystals
  123. 7.5: Imperfections in Solids
  124. 7.5.1: Imperfections
  125. 7.6: Silicates
  126. 7.6.1: Silicon
  127. 7.7: Thermodynamics of Ionic Crystal Formation
  128. 7.7.1: Lattice Energy
  129. 7.7.2: Lattice Energy - The Born-Haber cycle
  130. 7.7.3: Lattice Enthalpies and Born Haber Cycles
  131. 7.7.4: The Born-Lande' equation
  132. 7.P: Problems
  133. 8: Chemistry of the Main Group Elements
  134. 8.1: What are the main group elements and why should anyone care about them?
  135. 8.2: General Trends in Main Group Chemistry
  136. 8.2.1: The Periodic Table is an Organizing Concept in Main Group Chemistry
  137. 8.2.1.1: The metal-nonmetal-metalloid distinction and the metal-nonmetal "line" are useful for thinking about trends in elements' physical properties
  138. 8.1.1.2: There are qualitative differences between the chemistry of the elements in the first two rows and those in the rest of the periodic table
  139. 8.2.2: Electronegativity increases and radius decreases towards the upper left of the periodic table, with electron withdrawing substituents, and with oxidation state
  140. 8.2.3: Ionization energy roughly increases towards the upper left of the periodic table but is also influenced by orbital energy and pairing energy effects
  141. 8.2.4: As may be seen from considering an element's redox diagrams, main group elements (aside from the noble gases) generally are more oxidizing towards the upper left of the periodic table and more reducing towards the lower right of the periodic table
  142. 8.2.4.1: Latimer Diagrams summarize elements' redox properties on a single line
  143. 8.2.4.2: Frost Diagrams show how stable element's redox states are relative to the free element
  144. 8.2.4.3: Pourbaix Diagrams are Redox Phase Diagrams that Summarize the most stable form of an element at a given pH and solution potential
  145. 8.3: Group 1, The Alkali Metals
  146. 8.3.1: Alkali Metals' Chemical Properties
  147. 8.4: Hydrogen
  148. 8.4.1: Hydrogen's Chemical Properties
  149. 8.5: Group 2, The Alkaline Earth Metals
  150. 8.5.1: Preparation and General Properties of the Alkaline Earth Elements
  151. 8.5.2: Alkaline Earth Metals' Chemical Properties
  152. 8.6: Group 13 (and a note on the post-transition metals)
  153. 8.6.1: Properties of the Group 13 Elements and Boron Chemistry
  154. 8.6.2: Heavier Elements of Group 13 and the Inert Pair Effect
  155. 8.7: Group 14
  156. 8.7.1: The Group 14 Elements and the Many Allotropes of Carbon
  157. 8.7.2: Inorganic Compounds of the Group 14 Elements
  158. 8.7.3: Chemistry of Carbon (Z=6)
  159. 8.7.4: Chemistry of Silicon (Z=14)
  160. 8.7.4.1: Silicates
  161. 8.7.4.2: Silicon and Group 14 Elements
  162. 8.7.5: Chemistry of Germanium (Z=32)
  163. 8.7.6: Chemistry of Tin (Z=50)
  164. 8.7.7: Chemistry of Lead (Z=82)
  165. 8.7.7.1: Lead Acetate
  166. 8.7.7.2: Lead Plumbate
  167. 8.8: Group 15
  168. 8.8.1: The Group 15 Elements
  169. 8.8.2: Compounds of the Group 15 Elements
  170. 8.9: The Nitrogen Family
  171. 8.9.1: General Properties and Reactions
  172. 8.9.1.1: Nitrogen Group (Group 5) Trends
  173. 8.9.2: Chemistry of Nitrogen (Z=7)
  174. 8.9.3: Chemistry of Phosphorus (Z=15)
  175. 8.9.4: Chemistry of Arsenic (Z=33)
  176. 8.9.5: Chemistry of Antimony (Z=51)
  177. 8.9.6: Chemistry of Bismuth (Z=83)
  178. 8.9.7: Chemistry of Moscovium (Z=115)
  179. 8.10: Group 16
  180. 8.10.1: The Group 16 Elements
  181. 8.10.1.1: Compounds of the Group 16 Elements
  182. 8.10.1.2: The Group 16 Elements
  183. 8.11: The Oxygen Family (The Chalcogens)
  184. 8.11.1: General Properties and Reactions
  185. 8.11.1.1: Oxygen Group (Group VIA) Trends
  186. 8.11.2: Chemistry of Oxygen (Z=8)
  187. 8.11.2.1: Ozone
  188. 8.11.3: Chemistry of Sulfur (Z=16)
  189. 8.11.4: Chemistry of Selenium (Z=34)
  190. 8.11.5: Chemistry of Tellurium (Z=52)
  191. 8.11.6: Chemistry of Polonium (Z=84)
  192. 8.11.7: Chemistry of Livermorium (Z=116)
  193. 8.12: Group 17 (The Halogens)
  194. 8.12.1: Compounds of the Group 17 Elements (Halogens)
  195. 8.12.2: The Group 17 Elements (Halogens)
  196. 8.13: The Halogens
  197. 8.13.1: Physical Properties of the Halogens
  198. 8.13.1.1: Atomic and Physical Properties of Halogens
  199. 8.13.1.2: General Properties of Halogens
  200. 8.13.1.3: Halogen Group (Group 17) Trends
  201. 8.13.1.4: Physical Properties of the Group 17 Elements
  202. 8.13.2: Chemical Properties of the Halogens
  203. 8.13.2.1: Halide Ions as Reducing Agents
  204. 8.13.2.2: Halogens as Oxidizing Agents
  205. 8.13.2.3: Interhalogens
  206. 8.13.2.4: More Reactions of Halogens
  207. 8.13.2.5: Oxidizing Ability of the Group 17 Elements
  208. 8.13.2.6: Testing for Halide Ions
  209. 8.13.2.7: The Acidity of the Hydrogen Halides
  210. 8.13.3: Chemistry of Fluorine (Z=9)
  211. 8.13.4: Chemistry of Chlorine (Z=17)
  212. 8.13.4.1: The Manufacture of Chlorine
  213. 8.13.5: Chemistry of Bromine (Z=35)
  214. 8.13.6: Chemistry of Iodine (Z=53)
  215. 8.13.7: Chemistry of Astatine (Z=85)
  216. 8.14: The Noble Gases
  217. 8.14.1: History, usage, properties, and distribution of the elements
  218. 8.14.2: Properties of Nobel Gases
  219. 8.14.2.1: Noble Gas (Group 18) Trends
  220. 8.14.3: Chemistry of the Group 18 (Noble Gas) Elements
  221. 8.14.4: Reactions of Nobel Gases
  222. 8.14.5: Chemistry of Helium (Z=2)
  223. 8.14.6: Chemistry of Neon (Z=10)
  224. 8.14.7: Chemistry of Argon (Z=18)
  225. 8.14.8: Chemistry of Krypton (Z=36)
  226. 8.14.9: Chemistry of Radon (Z=86)
  227. 8.14.10: Chemistry of Xenon (Z=54)
  228. 8.P: Problems
  229. 9: Coordination Chemistry I - Structure and Isomers
  230. 9.1: Prelude to Coordination Chemistry I - Structure and Isomers
  231. 9.2: History
  232. 9.3: Nomenclature and Ligands
  233. 9.4: Isomerism
  234. 9.5: Coordination Numbers and Structures
  235. 9.6: Coordination Frameworks
  236. 9.P: Problems
  237. 10: Coordination Chemistry II - Bonding
  238. 10.1: Evidence for Electronic Structures
  239. 10.1.1: Thermodynamic Data
  240. 10.1.2: Magnetic Susceptibility
  241. 10.1.3: Electronic Spectra
  242. 10.1.4: Coordination Number and Molecular Shapes
  243. 10.2: Bonding Theories
  244. 10.2.1: Crystal Field Theory
  245. 10.3: Ligand Field Theory
  246. 10.3.1: Ligand Field Theory - Molecular Orbitals for an Octahedral Complex
  247. 10.3.2: Orbital Splitting and Electron Spin
  248. 10.3.3: Ligand Field Stabilization Energy
  249. 10.3.4: Tetrahedral Complexes
  250. 10.3.5: Square-Planar Complexes
  251. 10.4: Angular Overlap
  252. 10.4.1: Sigma Bonding in the Angular Overlap Model
  253. 10.4.2: Pi Acceptors in the Angular Overlap Model
  254. 10.4.3: Pi Donors in the Angular Overlap Model
  255. 10.4.4: The Spectrochemical Series
  256. 10.4.5: The Magnitude of Parameters eσ, eπ and Δ
  257. 10.4.6: The Magnetochemical Series
  258. 10.5: The Jahn-Teller Effect
  259. 10.6: Four- and Six-Coordinate Preferences
  260. 10.7: Other Shapes
  261. 10.P: Problems
  262. 11: Coordination Chemistry III - Electronic Spectra
  263. 11.1: Absorption of Light
  264. 11.1.1: Beer-Lambert Absorption Law
  265. 11.2: Quantum Numbers of Multielectron Atoms
  266. 11.2.1: Finding Microstates and Term Symbols
  267. 11.2.2: Spin-Orbit Coupling
  268. 11.3: Electronic Spectra of Coordination Compounds
  269. 11.3.1: Selection Rules
  270. 11.3.2: Correlation Diagrams
  271. 11.3.3: Tanabe-Sugano Diagrams
  272. 11.3.4: Symmetry labels for split terms
  273. 11.3.5: Applications of Tanabe-Sugano Diagrams
  274. 11.3.6: Tetrahedral Complexes
  275. 11.3.7: Charge-Transfer Spectra
  276. 11.3.8: Applications of Charge-Transfer
  277. 12: Coordination Chemistry IV - Reactions and Mechanisms
  278. 12.1: Introduction to Reactions of Metal Complexes
  279. 12.2: Substitutions Reactions
  280. 12.2.1: Introduction to Substitution Reactions
  281. 12.2.2: Inert and Labile Complexes
  282. 12.2.3: Mechanistic Possibilities
  283. 12.3: Kinetics Hint at the Reaction Mechanism
  284. 12.3.1: Rate Law for Dissociative Mechanisms
  285. 12.3.2: Rate Laws for Interchange Mechanisms
  286. 12.3.3: Rate Law for Associative Mechanisms
  287. 12.3.4: Preassociation Complexes
  288. 12.3.5: Activation Parameters
  289. 12.3.6: Some Reasons for Differing Mechanisms
  290. 12.4: Experimental Evidence in Octahedral Substitutions
  291. 12.4.1: Dissociation
  292. 12.4.2: Linear Free Energy Relationships
  293. 12.4.3: Associative Mechanisms
  294. 12.4.4: The conjugate base mechanism
  295. 12.4.5: The Kinetic Chelate Effect
  296. 12.5: Stereochemistry of Octahedral Reactions
  297. 12.5.1: Substitution in trans-en octahedral complexes
  298. 12.5.2: Substitution in cis-en octahedral complexes
  299. 12.5.3: Isomerization of Chelate Rings
  300. 12.6: Substitutions in Square Planar Complexes
  301. 12.6.1: Kinetics and Stereochemistry of Square Planar Reactions
  302. 12.6.2: Evidence for Associative Reactions
  303. 12.7: The Trans Effect
  304. 12.8: Redox Mechanisms
  305. 12.8.1: Outer Sphere Electron Transfer
  306. 12.8.2: Inner Sphere Electron Transfer
  307. 12.9: Reactions of Coordinated Ligands
  308. 12.9.1: Metal-catalyzed Hydrolysis
  309. 12.9.2: Template Reactions
  310. 12.9.3: Electrophilic Substitutions
  311. 13: Organometallic Chemistry
  312. 13.1: Introduction to Organometallic Chemistry
  313. 13.2: Nomenclature, Ligands, and Classification
  314. 13.3: Electron Counting in Organometallic Complexes
  315. 13.3.1: The 18 Electron Rule
  316. 13.3.2: Simplifying the Organometallic Complex by Deconstruction
  317. 13.4: Survey of Organometallic Ligands
  318. 13.4.1: Carbon Monoxide (Carbonyl Complexes)
  319. 13.4.2: Ligands similar to CO
  320. 13.4.3: Hydrides and Dihydrogen Complexes
  321. 13.5: Bonding between Metal Atoms and Organic Pi Systems
  322. 13.5.1: Linear π Systems
  323. 13.5.2: Cyclic π systems
  324. 13.5.3: Odd-numbered π Systems
  325. 13.5.4: Fullerene Complexes
  326. 13.6: Metal-Carbon Bonds
  327. 13.6.1: Metal Alkyls
  328. 13.6.2: Carbenes
  329. 13.6.3: Carbyne (Alkylidyne) Complexes
  330. 13.6.4: Carbido and Cumulene Complexes
  331. 13.6.5: Carbon Wires- Polyyne and Polyene Bridges
  332. 13.7: Characterization of Organometallic Complexes
  333. 14: Organometallic Reactions and Catalysis
  334. 14.1: Reactions Involving Gain or Loss of Ligands
  335. 14.1.1: Ligand Dissociation and Substitution
  336. 14.1.2: Oxidative Addition
  337. 14.1.3: Reductive Elimination
  338. 14.1.4: Sigma Bond Metathasis
  339. 14.1.5: Application of Pincer Ligands
  340. 14.2: Reactions Invloving Modification of Unsaturated Ligands
  341. 14.2.1: Introduction to Insertion
  342. 14.2.2: CO Insertions (Alkyl Migration)
  343. 14.2.3: Migratory Insertion-1,2-Insertions
  344. 14.2.4: β-Elimination Reactions
  345. 14.2.5: Abstraction and Addition
  346. 14.3: Organometallic Catalysts
  347. 14.3.1: Catalytic Deuteration
  348. 14.3.2: Hydroformylation
  349. 14.3.3: Monsanto Acetic Acid Process
  350. 14.3.4: Wacker (Smidt) Process
  351. 14.3.5: Hydrogenation by Wilkinson's Catalyst
  352. 14.3.6: Olefin Metathesis
  353. 14.4: Heterogeneous Catalysts
  354. 14.4.1: Ziegler-Natta Polymerizations
  355. 14.4.2: Water-Gas Shift Reaction
  356. 14.5: Problems
  357. 14.5.1: Concept Review Questions Chapter 12
  358. 14.5.2: Homework Problems Chapter 12
  359. 15: Parallels between Main Group and Organometallic Chemistry
  360. 15.1: Parallels between Main Group and Binary Carbonyl Complexes
  361. 15.2: The Isolobal Analogy
  362. 15.2.1: Extensions of the Analogy
  363. 15.2.2: Some Applications of the Isolobal Analogy
  364. 15.3: Metal-Metal Bonds
  365. 15.3.1: Metal-Metal Multiple Bonds
  366. 15.4: Cluster Compounds
  367. 15.4.1: Boranes
  368. 15.4.2: Heteroboranes
  369. 15.4.3: Metallaboranes and Metallacarboranes
  370. 15.4.4: Carbonyl Clusters
  371. 15.4.5: Carbon-Centered Clusters
  372. 15.4.6: Additional Comments on Clusters
  373. 15.5: Problems
  374. 16: Appendix
  375. 16.1: Periodic Table
  376. 16.2: Character Tables
  377. 16.3: Tanabe-Sugano Diagrams
  378. Back Matter
  379. Index
  380. Index
  381. Glossary
  382. Detailed Licensing