Activity 9A Substitution Reactions An incoming group replaces a leaving group Incoming groups can contain more than one

e atom Nucleophile Donates electrons Attracted to electron deficient or positive atoms The incoming group is a nucleophile Electrophile Accepts electrons Attracted to electron rich or negative atoms The carbon they bind the leaving and incoming groups bind to is an electrophile One-Step Nucleophilic Substitution (SN2) Bimolecular 2 molecules present in the transition state Rate dependent on the concentrations of both reactants Transition State The highest potential energy species between the reactant and the products The dotted line represents a partial bond which suggests that the bonds are being formed and broken simultaneously o Reaction is said to be concerted because everything is happening at the same time The incoming group is on the opposite side of the leaving group Nucleophile approaches the side opposite the leaving group Nucleophiles Must have either a lone pair of electrons or a negative charge What makes a better nucleophile? Less electronegative compounds Negative charge is better than neutral Stronger bases More polarizable Less bulky/less hindered Electrophiles Must have either a positive charge or a partially positive center What makes a better leaving group? More polarizable Neutral Weak base More stable

Activity 9B Two-Step Nucleophilic Substitution (SN1) Step 1 is slow because a bond is breaking and the reaction proceeds from a stable reactant to a higher energy charged intermediate Rate determining step Step 2 is fast because the higher intermediate is reacting to form a neutral stable product Unimolecular One reactant involved in the rate determining step Carbocation Intermediates Formed in Step 1 Carbocation Structure is trigonal planar Carbon with the positive charge sp2 hybridization 6 valence electrons The carbocation is Electron deficient or positive Most likely to react with electron rich reagents Acts as a Lewis Acid 3 is the lowest energy General order of reactivity 3>2>1>>Methyl Retention of configuration is when the incoming group replaces the leaving group on the same side Inversion of configuration means that the incoming group replaced the leaving group on the opposite side Formed in greater amounts Rearrangements Any time a carbocation intermediate is formed rearrangements are possible