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Nucleophilic Substitution Reactions: Mechanisms Experimental data from nucleophilic substitution reactions on substrates that haveoptical activity (the

ability to rotate plane-polarized light) shows that two general mechanisms exist for these types of reactions. The first type is called an SN2 mechanism. This mechanism follows second-order kinetics (the reaction rate depends on the concentrations of two reactants), and its intermediate contains both the substrate and the nucleophile and is therefore bimolecular. The terminology SN2 stands for “substitution nucleophilic bimolecular.” The second type of mechanism is an SN1 mechanism. This mechanism follows first-order kinetics (the reaction rate depends on the concentration of one reactant), and its intermediate contains only the substrate molecule and is therefore unimolecular. The terminology SN1 stands for “substitution nucleophilic unimolecular.” SN2 mechanism The alkyl halide substrate contains a polarized carbon halogen bond. The SN2 mechanism begins when an electron pair of the nucleophile attacks the back lobe of the leaving group. Carbon in the resulting complex is trigonal bipyramidal in shape. With the loss of the leaving group, the carbon atom again assumes a pyramidal shape; however, its configuration is inverted. See Figure 1 below.

Figur e1 The SN2 mechanism can also be illustrated as shown in Figure 2 .

and this mechanism is sometimes illustrated as shown in Figure 3 . This inversion is often called the Walden inversion. the nucleophile's attack should be hindered and the rate . If a large number of groups are bonded to the same carbon that bears the leaving group. This occurs because the nucleophilic attack is always on the back lobe (antibonding orbital) of the carbon atom acting as the nucleus. going from starting material to product. Also notice that the nucleophile must always attack from the side opposite the side that contains the leaving group. the intermediate shows both the nucleophile and the substrate. SN2 mechanisms always proceed via rearward attack of the nucleophile on the substrate.Figur e2 Notice that in either picture. This process results in the inversion of the relative configuration. Figur e3 Steric hindrance SN2 reactions require a rearward attack on the carbon bonded to the leaving group.

Solvent effects For protic solvents (solvents capable of forming hydrogen bonds in solution). thus lowering its ground state energy. therefore.03 0 SN2 reactions give good yields on 1° (primary) alkyl halides. the rate of reaction increases. the rate of reaction. Figure 4 illustrates the effect of solvent polarity on the energy of activation and. the greater the steric hindrance and the slower the rate of reaction. . moderate yields on 2° (secondary) alkyl halides. and poor to no yields on 3° (tertiary) alkyl halides. This decrease occurs because protic solvents solvate the nucleophile. Polar aprotic solvents (solvents that cannot form hydrogen bonds in solution) do not solvate the nucleophile but rather surround the accompanying cation. thus. This phenomenon is called steric hindrance. unspecified nucleophile and leaving group. Because the energy of the activated complex is a fixed value. therefore. Different nucleophiles and leaving groups would result in different numbers but similar patterns of results. the energy of activation becomes greater and. thereby raising the ground state energy of the nucleophile. The larger and bulkier the group(s). the rate of reaction decreases. Table1 shows the effect of steric hindrance on the rate of reaction for a specific. the energy of activation becomes less and. Because the energy of the activated complex is a fixed value. an increase in the solvent's polarity results in a decrease in the rate of SN2 reactions.of the reaction slowed. TABL Effects of Steric Hindrance upon Rates E1 of SN2 Reactions Alkyl Group (ALK) −CH3(small group) −CH2CH3 (larger group) −CH(CH3)2 (bulky group) −C(CH3)3 (very bulky group) Relative Rate of Substitution 30 1 0.

Carbocations contain sp2 hybridized orbitals and thus have planar structures. The second step (the fast step) involves the formation of a bond between the nucleophile and the alkyl carbocation. so a nucleophile attack is equally possible from either side of the plane. S N1 mechanisms proceed via a carbocation intermediate. a pure. Because the activated complex contains only one species—the alkyl carbocation—the substitution is considered unimolecular. The first step (the slow step) involves the breakdown of the alkyl halide into an alkyl carbocation and a leaving group anion. SN1 mechanism The second major type of nucleophilic substitution mechanism is the SN1 mechanism.Figur e4 The smaller activation energy leads to the more rapid reaction. This mechanism proceeds via two steps. Therefore. optically active .

Figur e5 . as shown in Figure 5 .alkyl halide undergoing an SN1 substitution reaction will generate a racemic mixture as a product.