CHAPTER1:ELECTRONICSTRUCTURESAND

BONDING

Organic Chemistry is the study of carbon compounds.

The Uniqueness of Carbon

Atomicstructure
Atomic number (Z): number of protons in the nucleus of an atom.

Mass number (A): total number of protons and neutrons in the

nucleus of an atom.

Isotopes: have the same Z but different mass numbers.

Atomic orbitals: region of space around the nucleus where the

probability of finding an electron is very high.
AOshavecharacteristicshape,sizeandenergy.Orbitalsthathave
thesameenergyaredegenerateorbitals.

Electron configuration of atoms

Rule 1 (aufbau principle): orbitals are occupied in order of
increasing energy (1s<2s<2p<3s<3p<4s<3d.)

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 Rule 2 (Paulis exclusion principle): only 2 electrons can
occupy an orbital and they must have opposite spin ( ).
Rule 3 (Hunds rule): when there are degenerate orbitals, one
electron is added to each with their spins parallel until all are half
full. Then a second electron with opposite spin is added to each
degenerate orbital.

Octect rule: tendency to have 8 electrons in the outermost

(valence) shell, which is a very stable, noble-gas, configuration.
Hydrogen only requires a duet (2 electrons) to achieve He
electronic configuration. Exceptions to the octect rule: for example
BF3 and PCl5

Chemical bonds
Ionic bonds: formed by the transfer of one or more electrons
from one atom to another to create ions, which electrically attract
each other.

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 Li
-e Li with filled shell
Li F
ionic compound
F
+e F with filled shell
(octet)

Ionization energy: energy required to remove an electron from

an atom.

Electron affinity: energy released when an atom acquires an

electron.

Electronegativity: ability of an atom to attract electrons.

Dipole moment ()=magnitude of charge (e) x distance between

charges (d) Partial positive and negative charges are
represented by + and - or by an arrow with the tip pointing to
the more electronegative atom.

Covalent bonds: formed when atoms share electrons.

Non-polar covalent bonds: the electrons are equally shared. The

electronegativity of the two atoms is the same or very similar
(example: Cl2). The net dipole moment equals zero.

F F F F covalent compound

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 Polar covalent bonds: the electrons are not equally shared. The
electronegativity of one atom is greater than the other.

(example: HCl). The net dipole moment is greater than zero.

Representation of structure

Lewis dot structures: represent the valence electrons of an atom

by dots (non-bonding) and dashes (bonding electrons).

Kekul or line-bond structures: each dash represents a pair of

electrons. Non-bonding electrons are omitted.

Condensed structures: omit bonding/nonbonding electrons.

Skeletal structures: Omit hydrogens attached to carbon. Carbons

are represented by intersection of straight lines as well as the the
end of a line. Hydrogens that are connected to atoms other
than carbon MUST be drawn! For instance OH, SH, NH2, etc.

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 Formal charges: calculated by subtracting the number of
valence electrons (nonbonding + 1/2 bonding) of an atom in its
bonded state from the number of valence electrons it has as a
neutral free atom.

Atomic orbitals
s orbitals have spherical shape. The 2s orbital contains a
node (region where the probability of finding an electron is
zero)

p orbitals have dumbbell shape and have 3 possible

orientations in space: px, py, pz (degenerate orbitals) 2p
orbitals contain a nodal plane.

Molecular Orbital Theory

for example H2 and F2 molecules.
Molecular orbitals: result from the combination of AOs
bonds: are cylindrically symmetrical and result from head-on
overlap of AOs (s or p)

bonds: result from sideways overlap of AOs (p)

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 Bond length: distance between two nuclei that leads to
maximum bond stability.

Bond strength (or bond dissociation energy): energy released

when the bond is formed (or energy required to break a bond). It
measures the stability of a bond.

Bonding molecular orbitals ( : have increased electron

density between the nuclei

Antibonding molecular orbitals ( : contain a node between

the nuclei

sp3 Hybridization: bonding in molecules where atoms form

only single bonds

H
- Tetrahedral molecule
H C H
- Bond angles: 109.5o
H

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 One 2s and three 2p atomic orbitals combine (hybridize) to
form four identical sp3 hybrid orbitals with tetrahedral
orientation (angles 109.5o).

Bonding in CH4 and CH3CH3: overlap head-on of all sp3

hybrid orbitals to form all bonds. Carbon-carbon single bond
strength is 88 kcal/mol, bond length is 1.54 .

sp2 Hybridization: bonding in molecules containing a double

bond

H H - Planar molecule
C C
H H - Bond angles: 120o

One 2s and two 2p atomic orbitals combine (hybridize) to form

three identical sp2 hybrid orbitals with triangular planar orientation
(angles 120o). The remaining 2p orbital is perpendicular to the sp2
plane.

Bonding in CH2CH2: the three sp2 hybrid orbitals overlap head-

on to form bonds. The unhybridized 2p orbitals overlap
sideways to produce one bond. C=C bond strength is 152
kcal/mol, bond length is 1.33 .

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 sp Hybridization: bonding in molecules containing an atom
with a triple bond or two double bonds

H C C H - Linear molecule
- Bond angles: 180o

One 2s and one 2p atomic orbitals combine (hybridize) to form

two identical sp linear hybrid orbitals (angle 180o) on the x-axis.
The two remaining 2p orbitals are perpendicular on the y and z
axis.
Bonding in CHCH: the two sp hybrid orbitals overlap head-on
to form bonds. The unhybridized 2p orbitals overlap sideways to
produce two bonds. C C bond strength is 200 kcal/mol
(strongest!), bond length is 1.20 (shortest!).

Bonding in CH3+, CH3, CH3-

The carbon atoms in both CH3+ and CH3 are sp2 hybridized.
The remaining unhybridized p orbital is perpendicular to the plane
of the sp2 orbitals, and it is empty in CH3+ while contains one
unpaired electron in CH3

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 The carbon atom in CH3- is sp3hybridized. Three sp3 orbitals
overlap head-on to form bonds and the fourth sp3 orbital
contains a pair of nonbonding electrons.

Atomic and Hybrid Orbitals:

Atomic Orbitals Hybrid Orbitals

109.50
+ =

2s 2p sp3
tetrahedral

1200
+ =

2s 2p sp2
trigonal planar

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 1800

+ =

2s 2p sp
linear

# of Domains Hybridization Geometry Bond

Angle
bonding non-
bonding

2 0 sp Linear 1800

3 0 sp2 Trigonal 1200

Planar

2 1 sp2 Bent ~1170

4 0 sp3 Tetrahedral 109.50

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 3 1 sp3 Trigonal ~1070
Pyramidal

2 2 sp3 Bent ~1050

ShowtheMolecularGeometryaroundthecentralatom,
Hybridization,andapproximatebondanglesinthefollowing
molecules.

SCNOH
Molecular Geometry hybridi- bond
around Central Atom zation angle

<) SCN = ______

<) CNO = ______
<) NOH = ______

a b c
CF3CH=C=O
Molecular Geometry hybridi- bond
around Central Atom zation angle
ab
< FCC = ______
)
abc
<) CCC = ______
bc
<
) CCO = ______

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 ab c
NCCH2CHO
Molecular Geometry hybridi- bond
around Central Atom zation angle
ab
<) NCC = ______
abc
< ) CCC = ______
bc
<) CCO = ______

ConstitutionalIsomers:Twocompoundsthathavethesame
molecularformulabuthavedifferentconnectivities.

Examples:

CH3OCH3 and CH3CH2OH

ClCH2CH2Cl and Cl2CHCH3

CH2=CHCH=CH2 and CH3CCCH3

and CH3CH2CH=CH2

ThreedimensionalFormulas:
Adashedwedgerepresentsabondthatprojectsbehindthemain
planeofthemolecule.

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 Asolidwedgerepresentsabondthatprojectsinfrontofthe
mainplainofthemolecule.

Anordinarylinerepresentsabondthatliesinthemainplaneof
themolecule.

Forexample:themoleculeofmethaneistetrahedral.

Resonance:

Delocalized electrons are electrons that are shared by more than 2

atoms.

The structure of benzene

Kekul structures: Actual structure:

Benzene is planar. Each carbon atom is sp2 hybridized and makes

3 bonds with two other carbon atoms and one hydrogen atom.
The unhybridized p orbitals are parallel and overlap sideways,
forming a doughnut shaped orbital above and below the plane of
the ring.

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The electrons are therefore shared by all six carbon atoms
delocalized. Electron delocalization occurs only when all atoms
sharing the delocalized electrons lie in the same plane, so their p
orbitals can effectively overlap.

A compound with delocalized electrons is said to have resonance.

Each approximate structure using localized electrons is called a
resonance structure or resonance contributor. The actual structure
is called a resonance hybrid (average of all resonance structures).

resonance
resonancecontributors hybrid

Drawing resonance contributors

The electrons in one resonance contributor are moved to generate

the next resonance contributor.

Rules for drawing resonance contributors:

1. only or nonbonding electrons move
2. the total number of paired or unpaired electrons does not change
3. move electrons towards an sp2 hybridized atom (a positive
charge, a bond or a radical), or a sp3 hybridized atom with
nonbonding electrons.
Examples:

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 + +
CH3CH CH CHCH3 CH3CH CH CHCH3 CH3CH CH CHCH3
resonancecontributors resonancehybrid

- +
CH3CH CH NHCH3 CH3CH CH NHCH3 CH3CH CH NHCH3
resonancecontributors resonancehybrid

O O O -
+
CH3C CH CHCH3 CH3C CH CHCH3 CH3C CH CHCH3
resonancecontributors resonancehybrid

Problem: Which of the following molecules have delocalized

electrons?

O
O

Draw all the important resonance structures for the following ions showing all lone pairs of
electrons and formal charges. Show the electron flow by using arrows for full credit.

Predicted stabilities of resonance contributors

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Each resonance contributor may be more stable than another and
therefore is a better description of the overall molecular structure.
The greater the predicted stability of the resonance contributor, the
more it contributes to the resonance hybrid.
Factors that increase the predicted stability of a contributing
resonance structure:
1. all atoms have an octet
2. negative charges are on the most electronegative atoms (and
positive charges on the least electronegative atoms)
3. charge (and/or charge separation) can be destabilizing

Resonance energy is the extra stability a compound gains for

having delocalized electrons
In general:
1. The greater the number of relatively stable resonance
contributors, the greater the resonance energy.
2. The more nearly equivalent the resonance contributors, the
greater the resonance energy.

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