Electron Withdrawing and Electron Donating Groups

Certain atoms or groups of atoms can add or withdrawal electron density to a system. Electron withdrawing groups (EWG) remove electron density from a system and tend to stabilize anions or electron rich structures. Conversely, EWG destabilize cations or electron poor structures. Electron donating groups (EDG) add electron density to a system and tend to stabilize cations or electron poor systems. Conversely, EDG destabilize anions or electron rich systems. There two ways electron density can distribute itself through a molecule. It can move through -bonds or through -bonds. The movement of electron density through -bonds is called inductive effects. The movement of electron density through -bonds is called resonance effects. Whether an atom or group of atoms is ED or EW by inductive effects or resonance effects depends on certain physical features such as electronegativity, lone pair electrons, and the presence of multiple bonds.

Groups that are EWG inductively but EDG through resonance. These are electronegative atoms with lone pair electrons
X

Groups that are EDG only by inductive effects. Alkyl groups, the more branched, the more donating
CH3 CH2CH3 CH(CH3)2

OH NH2

Groups that are EWG only by inductive effects. Atoms with no lone pair electrons but have a partial positive charge or a formal +1 charge.
F C F F H H +

Groups that are EWG by resonance. The atom that is attached to the molecule is involved in a multiple bond.

O CH O C R C N O C OR

N H

Groups that are EWG inductively and EWG Groups that can be either EWG or EDG by by resonance. resonance.

+ O N = -NO2 O

C CH2 H

Inductive effects, withdrawing or donating, weaken substantially when remove by more than two s bonds. Thus, inductive effects occur close to the atom or group of atoms that cause the inductive effect (e.g. one of the groups in the table above). Resonance effects can delocalize formal charges over a larger area; therefore, resonance effects are usually are more pronounced, i.e. they can donate or remove more electron density than inductive groups.

Examples: Which hydrogen in the molecules below is the most acidic?

O a) CH3CH2CH2C N b) CH3COCH3 c) HOCHCH2CH2CH2OH F

Approach: Since strong acids have weak (or stable) conjugate bases, EWG will make an acid stronger since it helps stabilize the conjugate base. Therefore, look for EWG in the structure above and the more acidic hydrogens should be near-by. For structure a), the nitrile functional group makes the protons on the adjacent carbon the most acidic because the resulting anion is stabilized by resonance.
_ CH3CH2 C C N H CH3CH2 C C N H _