I. Chemical Bonding and Electronic Structure Electronic configuration and valence Aufbau principle Valence shell and core shells Noble gas configuration and 8 electron rule Covalent vs ionic bonding Definition of terms Electron count in covalent bonds Multiple covalent bonds Atomic orbitals and hybridization VSEPR principle and bonding geometry Tetrahedral geometry and atomic orbitals Hybridization of atomic orbitals sp 3 , sp 2 and sp hybridization of carbon inclusion of lone pairs in VSEPR model Sigma and \(\pi\) bonding Electronegativity and polarization of covalent bonds Resonance Formal charge, hypovalency and hypervalency Conjugation of \(\pi\) electrons Aromaticity II. Functional groups and Nomenclature Hydrocarbons Alkanes Cycloalkanes Alkenes, dienes and polyenes Alkynes Arenes Haloalkanes Ethers, Sulfides and Epoxides Amines Alcohols Carbonyls Aldehydes Ketones Carboxylic acids Carboxylic acid derivatives Esters Amides Acid Halides Anhydrides Nitriles Imides Esters of inorganic acids: phosphates, sulfates, nitrates IUPAC rules for nomenclature Hydrocarbon rules Unsaturation Functional group prioritization Suffixes and substituent names for functional groups III. Stereochemistry Definition of terms: stereoisomer, chirality, conformation, configuration Conformational isomerism alkanes cyclohexane substituted cyclohexane Molecular chirality and optical activity Configurational isomerism Stereogenic carbon and the Cahn-Ingold-Prelog system Enantiomers and diastereomers E and Z alkenes cis- and trans- disubstituted cycloalkanes Stereogenicity in atoms other than carbon IV. Intermolecular interactions and physical properties Boiling point and melting point Effect of molecular weight Polarity and dipole-dipole interactions Hydrogen bonding interactions and their effect Solubility Solvent-solute interactions Dipole-dipole Hydrogen bonding The hydrophobic effect Chromatography Exploitation of intermolecular interactions Common stationary phases: silica and alumina forms: TLC, column, HPLC and size exclusion V. Reactive intermediates: carbocations, carbanions, free radicals Carbocations Trivalent carbon Lack of an octet sp2 hydridization empty p orbital Stability trends Resonance stabilization By neighboring \(\pi\) electrons By neighboring heteroatoms with lone pairs Carbanions Lone pair on carbon Retention of geometry Configurational lability Stability trends Free radicals Lack of an octet on C Neutrality of free radicals Stability trends VI. Spectroscopy Infrared Theory Symmetry, dipole moments and intensity Characteristic stretching frequencies Bending and other vibrational motion Mass spectrometry Theory Ionization methods Fragmentation reactions alpha cleavage beta cleavage McLafferty rearrangement Isoto\(\pi\)c distribution NMR Theory Chemical shift, deshielding and electronegativity Diamagnetic anisotropy Vicinal coupling Idea Coupling constant Multiplicity (N+1 rule) Effects of geometry on coupling constant Geminal and 4-bond coupling 13C NMR Other nuclei (15N, 31P, 19F) Integrated spectroscopy problems VII. Reactivity and the movement of electrons Lewis acids and bases; nucleophiles and electrophiles Definition of terms: addition, elimination, substitution Donation of electrons toward covalent bond Use of curved arrow formalism to describe electron movement Starts at reactive lone pair (or bond) Terminates at midpoint of forming bond Alternatively, ends at atom if changing charge state Curved arrows in resonance Kinetics and Thermodynamics Reversibility and irreversibility Le Chatelier’s Principle Kinetics and transition state energies Hammond’s postulate and the use of intermediates VIII. Acid-Base Reactivity Lewis acidity/basicity vs. Brønsted acidity/basicity Factors affecting Brønsted acidity Electronegativity Bond strength to hydrogen Inductive effects Resonance effects Solvent effects Quantifying acidity: pKa values Representative pKa values of various functional groups Solvents and the leveling effect