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Structural Effects

1. Resonance (Pi Electron Delocalization) Localized electrons are electrons that are restricted in a particular region. They belong to a single bond or a double bond. However, not all electrons are localized. Organic compounds contain delocalized electrons. Delocalized electrons do not belong to a single atom nor are confined to a bond between two atoms, but are shared by three or more atoms. The existence of delocalized electrons explains the behavior of organic compounds. Benzene, a cyclic six-membered ring with a molecular formula of C6H6, is an example of a compound that has delocalized electrons. Initially, it's structure was thought to contain alternating single and double bonds. However, this was disproved when modern analytical techniques showed that benzene is a planar molecule and the six C-C bonds have the same length. The length of each C-C bond is shorter than a C-C single bond but longer than a C-C double bond. If the C-C bonds in benzene all have the same length, they must also have the same number of electrons between the carbon atoms. This can happen only if the pi electrons of benzene are delocalized around the ring rather than each pair of pi electrons being localized between two carbons. The bonding in benzene can explain how the electrons can be delocalized. Each of benzene's six carbon atoms is sp2 hybridized. Each of its carbon uses two sp2 orbitals to bond to two other carbons; the third sp2 orbital overlaps the s orbital of a hydrogen. Each carbon also has a p orbital at right angles to the sp2 orbitals. The six p orbitals are parallel because benzene is planar. The p orbitals are close enough for side-to-side overlap, so each p orbital overlaps the p orbitals on both adjacent carbon. As a result, the overlapping p orbitals form a doughnut-shaped cloud of electron above and below the benzene ring. Below is a picture of benzene:

Each of the six pi electrons is not localized. Instead, each pi electron is shared by all six carbons. The six pi electrons are delocalized - they roam freely in the doughnut-shaped clouds that lie above and below the ring. To symbolize the delocalized electrons, benzene can be represented by a hexagon with dashed lines or a circle. Below is a picture:

Resonance is a structural effect that can be seen in systems where there are atoms that are sp2 hybridized. It is also called pi-electron delocalization. The concept of electron delocalization is used to explain resonance. Below is a picture of carbon trioxide (CO3) and its resonance structure:

In CO3, one of the oxygen atoms forms a double bond with carbon. However, this double bond is not limited to a particular carbon. The electron of carbon that is bonded to the oxygen atoms bonds to another oxygen atoms thereby breaking its bonds with the previous oxygen atom. The oxygen atoms that was used to be bonded to the carbon atoms gains a lone pair and obtains a charge of negative one (-1). This process also happens to the last oxygen. The three resonance structures of CO3 are called resonance contributors. Notice that the only difference between them is the placement of the double bond and of the lone pair. The structures are also represented by a doubleheaded arrow, indicating that the final structure of the compound revolves in them all. However, the final structure of CO3 is not among these. CO3's final structure represents the double bonds as dashed lines rather than solid lines to show the electron delocalization. This final structure is called the resonance hybrid. Resonance Stabilization: Delocalized electrons stabilize a compound. The extra stability that a compound gains from having delocalized electrons is called resonance stabilization.

The amount of resonance stabilization of a compound depends on the number and predicted stability of the resonance contributors. The greater the number of relatively stable resonance contributors and the more equivalent they are, the greater is the resonance stabilization.

Resonance stabilization involves lowering of energy. The delocalized molecular orbital is more stable than the localized molecular orbital because of the lower total energy of the delocalized molecular orbital. Types of Resonance Interaction: 1. unshared pair of electrons next to a pi bond

2. pi bonds between atoms of different electronegativity

3. involving a cycle of double bonds

4. involving an empty p orbital

Rules for Drawing Resonance Structures: 1. In drawing resonance structures, the nuclei of the atoms cannot be moved; only the electrons in the conjugated by orbitals may be moved. 2. Each resonance structure must have the same number of electrons and the same total charge.

3. The relative stability of the resonance structure can be judged by the same rules that govern Lewis structures (i.e. octet rule, location of formal charges, interaction between the charges in the structure). 4. The actual structure must resemble the most stable resonance contributor. 5. The resonance stability increases as the number of important (stable) structures increases. The greater number of contributing structures, the more stable is the final compound. Conjugation: Conjugation occurs in any molecules having a series of three or more adjacent overlapping p orbitals. Below are examples of compounds that undergoes conjugation:

Cinnamaldehyde

1,3 - pentadiene

copper phthalocyanine

2. C-H Hyperconjugation (Sigma Electron Release) C-H hyperconjugation is also called the sigma electron delocalization. It can be seen when a C-H (sp3) bond has a neighboring p orbital. It is commonly associated to methyl and other alkyl groups that are bonded to sp2 carbons. Unlike resonance, this is always an electron releasing effect ans is invoked to explain the relative stability of the carbocations through charge dispersal. Below is an illustration of the C-H hyperconjugative effect:

As a result of the sigma electron delocalization, the positive charge of is not concentrated on the carbon atom alone but is shared with three hydrogen atoms. There is a so-called charge dispersal resulting to stabilization of the carbocation. The actual ion is a hybrid of four contributing structures of comparative stability.

Being an electron releasing effect, C-H hyperconjugation is a stabilizing factor for both the carbocation and the carbon radical wherein carbon is electron deficient. 3. Inductive Effect Inductive effect is the distortion of the electron cloud due to the presence of electron attracting or electron repelling atoms and groups. A. Electron attracting groups a. Electronegative atoms or groups of atoms: -F, -O, -N, -Cl, -Br, -NO2, -NH2, -OH b. groups with orbital electronegativity: -C = CH, -C = N, -N = N c. groups with excess positive charge: -+NO2, -+NH3, -+R3 d. easily polarizable atoms: -I The presence of electron attracting group will cause distortion of the electron cloud from the carbon atoms by attracting the electron of the carbon atom towards them. Also, electron attracting groups cause transmission of inductive effect. B. Electron repelling groups a. groups with excess negative charge: -O-, -COO-

b. alkyl groups The presence of electron repelling groups will cause distortion of the electron cloud towards carbon. 4. Steric Effect Steric effect results from the presence of bulky groups. The bulky groups cause congestion and destabilization of molecules or ions. The greater the number of groups attached to a reaction center, the greater the destabilization. This congestion can be relieved by the twisting of bonds from their normal bond angles. 5. Intramolecular and Intermolecular H-bonding Intramolecular H-bonding occurs between the hydrogen atoms present in the compound with the electronegative compounds like fluorine, oxygen, and nitrogen atoms also present within the compound. This happens when the hydrogen atoms are close enough to the electronegative atoms to form hydrogen bonds. This can be observed in the ortho, meta, and para isomers of salicylic acid. Below are pictures of the different salicylic acid isomers:

In the ortho isomer, the hydrogen from the carboxyl group and the oxygen in the hydroxyl group can react to form a hydrogen bond. Another hydrogen bond can form between the hydrogen in the hydroxyl group and the oxygen in the carboxyl group. These hydrogen bonds can also happen in the meta isomer but the bond is relatively weaker compared to the ortho isomer because of the greater distance between the two functional groups. The relatively weakest intramolecular H-bonding happens in the para isomer because the distance of the carboxyl group and the hydroxyl group is at its greatest in the said isomer.

Intermolecular H-bonding occurs between the hydrogen atoms of one molecule and the electronegative atoms of another molecule. The strength of the intermolecular H-bonding is inversely proportional to the strength of the intramolecular bonding present in the compound. This is because the intramolecular hydrogen bonds weakens the ability of the molecule to form hydrogen bonds with other molecules. Therefore, the strongest intermolecular H-bonding exists in the para isomer, followed by the meta isomer, and the weakest in the ortho isomer.

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