In organic chemistry, hyperconjugation is the interaction of the electrons in a sigma bond

(usually C–H or C–C) with an adjacent empty (or partially filled) non-bonding p-orbital or
antibonding π orbital or filled π orbital, to give an extended molecular orbital that increases the
stability of the system.[1][2] Only electrons in bonds that are β to the positively charged carbon can
stabilize a carbocation by hyperconjugation.

Effect on chemical properties

Hyperconjugation has an effect on several chemical properties.[6][7]

1. Bond length: Hyperconjugation is suggested as a key factor in shortening of sigma bonds

(σ bonds) in such systems. For example, the single C–C bonds in 1,3-butadiene and
methylacetylene are approximately 1.46 angstrom in length, much less than the value
(1.54 angstrom) found in saturated hydrocarbons. This is due mainly to hyperconjugation
that gives partial double-bond character of the bond.

2. Dipole moments: The large increase in dipole moment of 1,1,1-trichloroethane as

compared with chloroform can be attributed to hyperconjugated structures.

3. The heat of formation of such molecules are greater than sum of their bond energies; and
the heats of hydrogenation per double bond are less than the heat of hydrogenation of
ethylene.
4. Stability of carbocations:

(CH3)3C+ > (CH3)2CH+ > (CH3)CH2+ > CH3+

The C–C σ bond adjacent to the cation is free to rotate, and as it does so, the three C–H σ
bonds of the methyl group in turn undergoes the stabilization interaction. The more
adjacent C-H bonds are, the larger hyperconjugation stabilization is.
[edit] Hyperconjugation in unsaturated compounds

Early studies in hyperconjugation were performed by Kistiakowsky et al. Their work, first
published in 1937, was intended as a preliminary progress report of thermochemical studies of
energy changes during addition reactions of various unsaturated and cyclic compounds. This
pioneering work would lead many to investigate the group’s puzzling findings.

Kistiakowsky and fellow researchers collected heats of hydrogenation data during gas-phase
reactions of various species containing one double bond. When comparing the addition of
hydrogen to propylene, 1-butene, 1-heptene, t-butyl ethylene, neopentylethylene, and finally
isopropylethylene the respective methyl, ethyl, n-amyl, isopropyl, t-butyl, and neopentyl groups
are equally effective in decreasing the want of the double bond for the addition of hydrogen. The
ΔH of values of three compounds in the form of R2C=CH2 were found to be equal (within 0.2
Cal/mol).[8]

A portion of Kistiakowsky’s work involved a comparison of other unsaturated compounds in the

form of CH2=CH(CH2)n-CH=CH2 (n=0,1,2). These experiments revealed an important result;
when n=0, there is an effect of conjugation to the molecule where the ΔH value is lowered by 3.5
Cal. This is likened to the addition of two alkyl groups into ethylene. Kistiakowsky also
investigated open chain systems, where the largest value of heat liberated was found to be during
the addition to a molecule in the 1,4-position. Cyclic molecules proved to be the most
problematic, as it was found that the strain of the molecule would have to be considered. The
strain of five-membered rings increased with a decrease degree of unsaturation. This was a
surprising result that was further investigated in later work with cyclic acid anhydrides and
lactones. Cyclic molecules like benzene and its derivatives were also studied, as their behaviors
were different from other unsaturated compounds.[8]

Despite the thoroughness of Kistiakowsky’s work, it was not complete and needed further
evidence to back up his findings. His work was a crucial first step to the beginnings of the ideas
of hyperconjugation and conjugation effects.

[edit] Stabilization of 1,3-butadiyne and 1,3-butadiene

The conjugation of 1,3-butadiene was first evaluated by Kistiakowsky, a conjugative
contribution of 3.5 kcal/mol was found based on the energetic comparison of hydrogenation
between conjugated species and unconjugated analogues [8]. Rogers et al., who used the method
first applied by Kistiakowsky, reported that the conjugation stabilization of 1,3-butadiyne was
zero, as the difference of ΔhydH between first and second hydrogenation was zero. The heats of
hydrogenation (ΔhydH) were obtained by computational MP2 quantum chemistry method[9].

Another group led by Houk et al.[10], suggested the methods employed by Rogers and
Kistiakowsky was inappropriate, because that comparisons of heats of hydrogenation evaluate
not only conjugation effects but also other structural and electronic differences. They obtained
-70.6 kcal/mol and -70.4 kcal/mol for the first and second hydrogenation respectively by ab initio
calculation, which confirmed Rogers’ data. However, they interpreted the data differently by
taking into account the hyperconjugation stabilization. To quantify hyperconjugation effect, they
designed the following isodesmic reactions in 1-butyne and 1-butene.

Deleting the hyperconjugative interactions gives virtual states which have energies that are 4.9
and 2.4 kcal/mol higher than those of 1-butyne and 1-butene, respectively. Employment these
virtual states results in a 9.6 kcal/mol conjugative stabilization for 1,3-butadiyne and 8.5
kcal/mol for 1,3-butadiene.

Inductive effect

If the electronegative atom is then joined to a chain of atoms, usually carbon, the positive charge
is relayed to the other atoms in the chain. This is the electron-withdrawing inductive effect, also
known as the -I effect.
Some groups, such as the alkyl group are less electron-withdrawing than hydrogen and are
therefore considered as electron-releasing. This is electron releasing character and is indicated by
the +I effect.

As the induced change in polarity is less than the original polarity, the inductive effect rapidly
dies out, and is significant only over a short distance. The inductive effect is permanent but
feeble, as it involves the shift of strongly held σ-bond electrons, and other stronger factors may
overshadow this effect.

The inductive effect may be caused by some molecules also. Relative inductive effects have been
experimentally measured with reference to hydrogen.

Inductive effects can be measured through the Hammett equation.

Inductive Effect can also be used to determine whether a molecule is stable or unstable
depending on the charge present on the atom under consideration and the type of groups bonded
to it. For example, if an atom has a positive charge and is attached to a -I group its charge
becomes 'amplified' and the molecule becomes more unstable than if I-effect was not taken into
consideration. Similarly, if an atom has a negative charge and is attached to a +I group its charge
becomes 'amplified' and the molecule becomes more unstable than if I-effect was not taken into
consideration. But, contrary to the above two cases, if an atom has a negative charge and is
attached to a -I group its charge becomes 'de-amplified' and the molecule becomes more stable
than if I-effect was not taken into consideration. Similarly, if an atom has a positive charge and is
attached to a +I group its charge becomes 'de-amplified' and the molecule becomes more stable
than if I-effect was not taken into consideration. The explanation for the above is given by the
fact that more charge on an atom decreases stability and less charge on an atom increases
stability.

Hydrogen bond
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An example of intermolecular hydrogen bonding in a self-assembled dimer complex reported by Meijer
and coworkers.[1]

Intramolecular hydrogen bonding in acetylacetone helps stabilize the enol tautomer

A hydrogen bond is the attractive interaction of a hydrogen atom with an electronegative atom,
such as nitrogen, oxygen or fluorine, that comes from another molecule or chemical group. The
hydrogen must be covalently bonded to another electronegative atom to create the bond. These
bonds can occur between molecules (intermolecularly), or within different parts of a single
molecule (intramolecularly).[2] The hydrogen bond (5 to 30 kJ/mole) is stronger than a van der
Waals interaction, but weaker than covalent or ionic bonds. This type of bond occurs in both
inorganic molecules such as water and organic molecules such as DNA.

Intermolecular hydrogen bonding is responsible for the high boiling point of water (100 °C)
compared to the other group 16 hydrides that have no hydrogen bonds. Intramolecular hydrogen
bonding is partly responsible for the secondary, tertiary, and quaternary structures of proteins
and nucleic acids. It also plays an important role in the structure of polymers, both synthetic and
natural.

 F—H...:F (155 kJ/mol or 40 kcal/mol)

 O—H...:N (29 kJ/mol or 6.9 kcal/mol)
 O—H...:O (21 kJ/mol or 5.0 kcal/mol)
 N—H...:N (13 kJ/mol or 3.1 kcal/mol)
 N—H...:O (8 kJ/mol or 1.9 kcal/mol)
 HO—H...:OH+3 (18 kJ/mol[5] or 4.3 kcal/mol)