Professional Documents
Culture Documents
GeneralChemistry Lecture2
GeneralChemistry Lecture2
lecture 2
Electrophiles, nucleophiles
2
Plan for today
Catalysis
4
Nucleophiles and electrophiles
Equilibrium constant:
If Keq >> 1, then the reaction proceeds as written from left to right
If Keq ∼ 1, appreciable amounts of both reactant and product
are present at equilibrium
If Keq << 1, the reaction goes in the reverse direction, from right to left
Example:
Keq is relatively large, the reaction proceeds as written and greater than
99.99999% of the ethylene is converted into bromoethane
6
What determines the magnitude of
the equilibrium constant ?
The energy of the products must be lower than the energy of the reactants
= energy must be released
Gibbs free-energy change (DG) - the free energy of the products minus the
free energy of the reactants :
DG = Gproducts − Greactants
For a favorable reaction, DG < 0 energy is lost by the chemical system and
released to the surroundings (usually as heat) – reaction is exergonic
means standard
conditions,
1 atm, 298 K 7
8
The free-energy change DG is made up of two terms
an enthalpy term, DH, and a temperature-dependent
entropy term, TDS
10
Describing a reaction: bond dissociation energies
The amount of energy needed to break a given bond to produce two radical
fragments when the molecule is in the gas phase at 25 °C is a quantity called
bond strength, or bond dissociation energy (D)
The heat is released (negative DH) when a bond is formed because the products
are more stable and have stronger bonds than the reactants. Conversely, heat is
absorbed (positive DH) when a bond is broken because the products are less stable
and have weaker bonds than the reactants
Exothermic reactions are favored by products with strong bonds and by reactants
with weak, easily broken bonds and vice versa for endothermic reactions
11
12
ATP (adenosine triphosphate) is “energy-rich” or
“high-energy” compound
ATP has relatively weak bonds that require a relatively small amount of heat to
break, thus leading to a larger release of heat when a strong new bond forms in a
reaction
13
14
Describing a reaction: Energy diagrams and transition states
For a reaction to take place, reactant molecules must collide and
reorganization of atoms and bonds must occur
Step 1
15
A hypothetical transition state structure for the first step of the reaction of
ethylene with HBr. The C=C p bond and H−Br bond are just beginning to
break, and the C − H bond is just beginning to form
Many organic reactions have activation energies in the range 40 to 150 kJ/mol
(10–35 kcal/mol)
The reaction of ethylene with HBr has an activation energy of approximately 140
kJ/mol (34 kcal/ mol)
Reactions with activation energies less than 80 kJ/mol take place at or below
room temperature, while reactions with higher activation energies normally
require a higher temperature to give the reactants enough energy to climb the
16
activation barrier
Fast exergonic reaction Slow exergonic reaction
(small DG‡, negative DG°) (large DG‡, negative DG°)
17
18
Carbocation structure and stability
19
Inductive effects – electrons from a larger and more polarizable alkyl group can
shift toward a neighboring positive charge more easily than the electron from a
hydrogen resulting in stabilization of the cation
21
A more highly substituted carbocation forms faster than a less highly substituted
one and, once formed, rapidly goes on to give the final product
BUT :
22
The Hammond postulate (cont.)
Transition states (TS) are high-energy activated complexes that occur transiently.
We cannot observe transition states directly!
Hammond postulate says that we can get an idea of a particular transition state’s
structure by looking at the structure of the nearest stable species.
(a) Transition state for an endergonic reaction structurally resembles the product
(b) Transition state for an exergonic reaction structurally resembles the reactant
23
25
26
Electrophilic additions to conjugated dienes:
1,2- (Markovnikov) and 1,4-additions
27
28
more stable faster
Electrophilic additions to conjugated dienes:
effect of temperature
Electrophilic addition to a conjugated diene at or below room temperature normally
leads to a mixture of products in which the 1,2-adduct predominates over the
1,4-adduct. When the same reaction is carried out at higher temperatures,
the product ratio often changes and the 1,4-adduct predominates
29
30
Establishing equilibrium at higher temperatures via
reverse reaction
31
32
Conclusions
33
Catalysis
Catalyst allows the increase of the reaction rate
Heterogeneous catalysis
36
Homogeneous catalysis
Catalytic reagents
37
Enzymatic catalysis
Key principles:
• TS stabilization
• Shape complementarity
• Electrostatic complementarity
• Nucleophilic catalysis
• General acid – general base catalysis
• Proximity effects, strain, desolvation
Cofactors:
40
41
42
43
44
45
46
47
48
Lewis acid catalysis
Metal ion catalysis
49
50
Lewis acid catalysis
Example 1: ATPase
51
52
Lewis acid catalysis
Interactions enable:
Orientation of the substrate (CO2) in a favorable position for the nucleophilic
attack
Increase of nucleophilicity of H2O bound to Zn(II)
Enzyme in its basic form (i.e., OH− bound to Zn(II)) = active form
53
54