Structure Determination

How can the structure of an unknown compound be determined?

Before modern analytical tools were developed (for organic chemists this means the

development of NMR (~1950s) or IR (first used ~1900, not readily obtained until mid 1900s),

the only experimental evidence for the identity of an organic compound was elemental analysis

A chemist could thus determine the % of various elements in an unknown sample

For example, if a sample had 1 part carbon and 4 parts hydrogen (CH4)

what is the constitution?

H H
H C H H H C
H H

How to test the possible structures?

1
 Structure Determination

In order to distinguish the possible constitutional isomers, experimentalists would react the
compound in a substitution reaction and detect the number of isomeric products

H H Cl
H C H H C Cl H C H Obtain 1 isomer

H H H

Same compound

H Cl H
H H C H H C Cl H C Obtain isomers

H H H

Different compounds

By reacting methane in a variety of reactions, it was determined that a monosubstitution

always produced only 1 isomer, therefore all 4 hydrogens must be equivalent

2
 Structure Determination

In addition to the constitution, however, what was the configuration?

How are the 4 equivalent hydrogens arranged in space?

H H
H C H H C H H
C H
H H H
H
Planar
Pyramidal
Tetrahedral

H H
H C Cl H C H C H
H Cl Cl H
H
Each possible configuration would generate only 1 isomer with monosubstitution

(thus the 4 hydrogens are at equivalent positions)

React twice
By logic, eventually a
Cl H tetrahedral geometry
Cl was proposed

H C Cl Cl C Cl H C H Cl C H C H
Cl Cl H Cl Cl
H H H
Two products
Two products
One product!
3
 Structure Determination

This was the state of affairs until the beginning of the 20th century,

for any new compound the elemental analysis was obtained and then the structure was
inferred by systematically running reactions or by comparing to analogous compounds

Could a model be developed to predict the structure of organic compounds?

In 1916 G.N. Lewis published a paper that hypothesized that bonding occurred by sharing
electron pairs between atoms (in contrast to ionic bonds)

We now call these structures Lewis dot structures

by explicitly designating all valence electrons as a dot

Only designate C
H B N O F
valence electrons

The constitution could thus be predicted by filling the outer shell of electrons for each atom
(second row atoms thus need 8 electrons and thus an octet rule)

H O H Two electrons shared

resonance
4
Filled outer shell for all atoms

 Structure Determination

Original course notes from Lewis (1902)

The cube indicated does not
indicate easily how multiple
bonds are formed, or what is
the angle between various
bonds

C C

C C
???

The Lewis dot structures work well to determine the

constitution of a molecule (atoms are bonded in a way
that allows a filled octet rule to form),

but does not indicate configuration
5
 Structure Determination

The intuitive arguments of Lewis to determine constitution by sharing electrons to form a

filled outer shell, however, were given mathematical basis by Heitler and London (1927)

Studied binding energy of H2 molecule

H H
Figure from Heitler and
If electron 1 was only
London*

associated with hydrogen 1
and electron 2 was only
associated with hydrogen 2

H1 e1 H2 e2
If electron constraint was
Calculated bond energy a
removed and each electron
fraction of actual

can interact equally with both
nuclei

e
H1 e 1 H2
2
Energetic basis for a bond

Calculated bond energy much -sharing of electrons between two atoms

closer to actual
*
W. Heitler, F.Z. London, Z. Physik, 1927, (44), 455-472
6
 Valence Bond Theory

The intuitive description proposed by Lewis where bonds are formed between two atoms by
sharing valence electrons in order to obtain a filled octet for the outer shell is basis of

Valence Bond Theory

This theory is still the underlying principle most organic chemists use to rationalize

chemical reactions and predict chemical properties

Two major results from valence bond theory:

1) Concept of Resonance

Resonance structures result from electrons being associated with different nuclei

For H-H molecule

e e
H1 e1 H2 e2 H1 e2 H2 e1 H1 e 1 H2 H1 H2 e1
2 2

MOL
=
c1
1
+
c2
2
+
c3
3
+
c4
4

Actual structure is a combination of all contributing structures

with appropriate weighting factors

Called principle of linear combination
7
 Resonance in Organic Compounds

What is resonance?

(also called delocalization)

Look at a nitro group

O
RNO2 R N
O

The negative charge on the oxygen could be placed on either oxygen using Lewis structures

O O
R N R N
O O

Which structure is correct?

It turns out neither structure is correct, but the charge is delocalized onto both oxygens

-This process of being able to delocalize the charge onto more than one atom is called resonance

(Resonance is a result of not being able to draw an accurate structure using one Lewis structure)

8
 Resonance in Organic Compounds

Rules of Resonance

1. All resonance structures must be valid Lewis structures

(e.g. cannot have 10 electrons on one carbon in one structure)

2. Only electrons move

(cannot move nuclei, only electrons

usually double bonds or lone pairs connected through an extended p orbital system)

3. Number of unpaired electrons must be constant

9
 Resonance in Organic Compounds

Concept of resonance allows explanation of a number of chemical properties

How does resonance explain acidity?

Consider pKa of organic molecules

pKa

CH3CH2OH CH3CH2O H 16

O O
H3C H3 C H 4.8

OH O
Resonates similar
to nitro group

Both structures place a negative charge on oxygen after loss of proton,

but the pKa difference is greater than 11

10
 Resonance in Organic Compounds

A carbonyl group is a common resonance source

O -H O O
H3C H3C H3C
O H O O

Once the acid is deprotonated, the negative charge is located on one oxygen

The charge can be delocalized (resonated) onto the other oxygen

Neither structure is correct,

but rather the negative charge can be delocalized over both oxygen atoms

Resonance structures are simply a result of one Lewis structure being incomplete in
describing the location of electrons

A double headed arrow always means two (or more) resonance forms

Two arrows mean two chemically distinct structures

11
 Resonance in Organic Compounds

Comparison of Electron Density for Ethoxide versus Acetate anion

O O O
CH3CH2OH CH3CH2O H3C H3C H3 C
OH O O

The excess negative charge is more stable on the acetate anion that can resonate,

thus the conjugate acid is more acidic

12
 Resonance in Organic Compounds

Resonance also allows explanation for the concept of electronegativity

Electrons in a chemical bond need not be shared equally between two nuclei

For H-Cl molecule

e e
H e1 Cl e2 H e2 Cl e1 H e1 Cl H Cl e1
2 2

MOL
=
c1
1
+
c2
2
+
c3
3
+
c4
4

Unlike with H2 where the 1 and 2 wavefunctions were more stable than the charged wave
functions, with HCl the 4 wave function is the most stable, therefore highest coefficient

The electrons are more stable closer to Cl than H, therefore the chlorine atom is said to be
more electronegative than the hydrogen atom

These resonance considerations therefore also cause bond dipoles in unsymmetrical bonds

13
 Electronegativity Tables

Linus Pauling first established values to associate with each element

(there have been many different values computed, but the trend is the same)

Elements toward the upper right hand of the periodic table are more electronegative

Also can predict the relative electronegativity of two atoms

by their relative placement in the periodic table

H (2.3)

Li (0.9)
Be (1.6)
B (2.1)
C (2.5)
N (3.1)
O (3.6)
F (4.2)

Cl (2.9)

H3C OH Br (2.7)

2.5
3.6

I (2.4)

The numbers are a relative indication of how much the electrons

are attracted to a certain atom

As the number becomes larger, the electrons are attracted more by that atom

14
 Resonance in Organic Compounds

The bond dipoles resulting from unsymmetrical bonds also can affect the acidity

O O pKa

H 4.8

H3C OH H3C O

O O
H 0.7

Cl3C OH Cl3C O

Anion with trichloroacetic acetate is stabilized by inductive effects from polarized C-Cl bonds

O
Cl
C O
Cl Cl

15
 Induction

Induction refers to electron movement through bonds

-All bonds between different atoms are polar and the electrons are closer to the more
electronegative atom on time average

As the electronegative atom is further removed, the inductive effect is less

(inductive stabilization is through bonds, therefore if there are more bonds

to transverse the effect is less)

O O
F Base F
OH O
H H H H

X
pKa

The electronegative
H
4.8

fluorine pulls electron
I
3.2
density away from
F
2.6
carboxylate

16
 Field Effect

Can have similar effect merely through space (field) rather than through bonds (inductive)

H Cl Cl H
H Cl Cl H
CO2H CO2H

Which is more acidic?

H Cl Cl H
H Cl Cl H
CO2 CO2

17
 Resonance in Organic Compounds

Important to Remember:

Not all resonance structures need to contribute equally

If two resonance structures are not of equal energy,

then they will not contribute equally to the actual structure

H H H H
N N
H H H H

Octet rule obeyed

Positive charge on
on all atoms
less electronegative
atom

This leads to major and minor contributors

18
 Resonance Forms

H H H H
N N
H H H H

Deeper blue color on carbon

(less charge on carbon)

Actual hybrid structure

19
 Resonance Forms

O O O O

H3C CH3 H3C CH3 H3C CH3 H3C CH3

major
minor
inconsequential
Only a resonance
form if spins are
paired

Not all resonance forms need to contribute equally, but rather a weighting factor is given to
each resonance form depending upon its importance to the actual form

Typically forms with more bonds are more important

(often due to forms with less bonds typically have atoms without an octet)

Placing charge on the more electronegative atoms is important

The number of paired electrons must be constant

20
 Resonance Forms

Factors affecting stability of resonance structures:

- Placement of charge

O O
H3 C CH2 H3 C CH2

minor
major

When the only difference is the location of formal charge,

structure is more stable when anion is placed on more electronegative atom

21
 Resonance Forms

- Amount of Charge

Also related to number of bonds in a structure

inconsequential

While structure with four formal charges shown is a valid resonance form, if structure is
dramatically higher in energy then it is practically an irrelevant resonance form

22
 Resonance Forms

- Octet rule is important

O O

Octet rule not obeyed

major

Having all atoms with a filled octet rule is more stable than a resonance form

that only has 6 electrons in one outer shell

Even if this requires a positive formal charge to be placed on a more electronegative atom

Second row atoms are always more stable with a filled outer shell

23
 Resonance Forms

Curved arrows represent movement of electrons

As already observed in acid/base reactions, a curved arrow indicates movement of electrons

O O O

Arrows always show where electrons are moving

Formal charges on atoms are a result of electrons moving

24
 Resonance Forms

Drawing resonance structures properly is an aid to predict location of electrons

Remember actual structure is a hybrid of all relevant resonance forms

These resonance forms allow a chemist to predict

where excess electron density is located in a molecule

Excess negative charge is located on three carbon atoms, not on all five equally
25
 Empirical Evidence for Resonance

Chemical properties of molecule are not like one resonance form

Have already observed this with acidity difference between ethanol and acetic acid

pKa

O O
H3C H3C H 4.8

OH O

CH3CH2OH CH3CH2O H 16

26
 Empirical Evidence for Resonance

Observe also with dipole values for compounds with resonance

H3C
N N O N N O
H3C N O
H3C

4.47 D

Interatomic distances do not correspond to single, double, or triple bonds

H3C CH3 H2C CH2

Each C-C bond is part single

and part double bond

27
 Valence Bond Theory

2) Second conceptual advancement with valence bond theory is idea of hybridization

To understand why the concept of hybridization was introduced we need to become

reacquainted about the structure of an atom and how bonds between different atoms form

An atom consists of three types of particles:

Proton (positively charged)

Neutron (neutral)

Electron (negatively charged)

Ironically the word atom comes from the Greek language meaning indivisible,

as it was thought to be the smallest particle that did not have smaller constituents

The number of protons determines the element (also is the atomic number)

Carbon therefore has 6 protons located in the nucleus

Usually the nucleus also contains an identical number of neutrons as protons

If the number is different it is called an isotope

These two particles have similar mass

(~1830 times greater than an electron)
28
 Consider a Carbon Atom

Nucleus means kernel of a nut

1 fm
Nucleus of atom

6 protons (red), 6 neutrons (blue)

Nucleus of atom
-held together by nuclear forces

(region where protons and neutrons reside)

Shell of atom

(region where electrons reside)

1

Nucleus size is ~2 fm (1 fm = 10-15 m), atom size is ~1 (1 = 10-10 m)

For an uncharged 12C atom, there are 6 protons, 6 neutrons and 6 electrons

Therefore the nucleus, which is responsible for ~3600/1 parts of the mass,

only encompasses ~1 x 10-15 part of the volume (remember V = 4/3 r3)

29
 Electrons

Unlike the protons and neutrons which are in the nucleus (a relatively fixed point)

we cannot say with certainty where an electron is located at a certain time

(Heisenberg uncertainty principle)

What we can say is that on time average the electrons are located in orbitals

(regions of space)

*much bigger region than the nucleus

The electrons are not randomly placed, nor do they reside in simple circular orbits

Schrdinger developed a formula that could describe the properties of the electrons

(called )

This wave function, , mathematically describes the shape of an orbital where the electrons
resides and the square of the wave function, 2, is proportional to the probability of finding
an electron in a given volume

30
 Electrons

Each electron is described by a set of four quantum numbers

(Pauli principle: no two electrons may have the same values of all four quantum numbers)

n
l

principal quantum number

Related to shape of orbital

Integral values, n = 1, 2, 3, etc.
Integral values, l = 0, 1, 2, (n-1)

Indicative of shell the electron resides
Therefore if n=1, l must be 0

If n=2, l can be either 0 or 1

Atoms where n=1 (H and He) are first shell

If n=3, l can be 0, 1 or 2

Atoms where n=2 (Li, Be, B, C, N, O, F, Ne)

Each value of l represents a different orbital shape

are second shell, and so on

l=0 is s orbital

The higher the value of n, the greater the l=1 is p orbital

average distance of the electron from l=2 is d orbital

nucleus and thus the greater the electrons l=3 is f orbital

energy

(naming or orbitals derives from description
from early spectroscopists of metal alkali lines
as sharp, principal, diffuse and fundamental)

31
 Electrons

Each electron is described by a set of four quantum numbers

(Pauli principle: no two electrons may have the same values of all four quantum numbers)

m1
s

Related to orientation of the orbital in space
Spin quantum number

(x, y, z coordinates in three dimensions)

Can only have two values (-1/2 or +1/2)

Has integral values l,., 0, ., +l By convention, the two possible spin states
Thus if l=0 then m1 must be 0
are typically indicated by either having the
If l=1, then m1 can be -1, 0, or +1
spins pointing up or down

If l=2, then m1 can be -2, -1, 0, +1, +2

Orbitals of the same shell (n) and shape (l) With two electrons, if the spins are opposite
have the same energy regardless of m1
they are stated to have paired spins, if the
(thus all 3 p orbitals in the same shell have spins are pointing in the same direction then
the same energy, 2px=2py=2pz)
they are stated to have unpaired spins

paired
unpaired

32
 Electronic Configuration

If the four quantum numbers are known for each electron, then the electrons can be placed
into their respective orbitals by knowing the relative energy difference

Since the first row atoms (H and He) have only one orbital (1s) it is fairly easy to write the
electronic configuration for these atoms (either have one electron or two paired electrons)

Consider the second row atoms

The second row has a total of 5 orbitals (1s, 2s, 2px, 2py, 2pz)

2p
The first shell orbitals are lower in
Energy
2s energy than second shell and p orbitals
in the 2nd shell are higher in energy
1s than s orbitals in the second shell

With Carbon (1s22s22p2), however, the question arises as to where the second 2p electron goes

Hunds rule: for a given electronic configuration, the state with the greatest number of
unpaired spins has the lowest energy

Therefore carbon is 1s22s22px12py1 where the spins are parallel
33
 Shape of Orbitals

Solutions of the Schrdinger equation (E = ) will describe the wave equation (),

since 2 = probability of finding electron it also describes the shape of orbitals

1s orbital

radial density plot
radial probability plot

!2 never goes to zero

4!r2"2

r r
(distance from nucleus) (distance from nucleus)

three-dimensional shape

34
 Shape of Orbitals

As the number of shells increases, the presence of nodes increases

(nodes are regions of space where there is zero probability of finding an electron)

The number of nodes is equal to one less than the principal quantum number

(therefore for n=1 there are 0 nodes, for n=2 there is 1 node, for n=3 there are 2 nodes)

All second shell orbitals thus have 1 node

2s
2px
2py
2pz
Actual shape is
p orbitals have node at the nucleus
different than typically
stylized dumbbell
shaped p orbitals

35
 Structure of Methane

Molecules are made by combining atomic orbitals to form bonding regions for the electrons

Using the outer shell orbitals of methane, the compound results from combining

the 2s, 2px, 2py and 2pz orbitals of carbon with the four 1s orbitals of hydrogen

The electronic configuration for atomic carbon thus has a lower energy 2s orbital

and three degenerate 2p orbitals that are each orthogonal to the others

The valence electrons will thus have 2 in the lower energy 2s orbital and 1 in each of the
degenerate 2px and 2py orbitals

To form the methane molecule, therefore the 1s orbital of each hydrogen

must form bonds with the orbitals that have electrons

This bonding model has many problems:

1) implies different energy and bond length of C-H bonds

2) Two of the C-H bonds must have a 90 bond angle

3) Have too many electrons in an orbital
36
 Hybridization Model for Bonding

Instead of using atomic orbitals for bonding, a different model considers first hybridizing the
atomic orbitals to form hybridized orbitals

Same rules apply for combining atomic orbitals to form hybrid orbitals

1) Get same number of hybridized orbitals as starting atomic orbitals used to form hybrid

2) Shape of hybridized orbitals is obtained by the mathematical addition of the wave

functions for the atomic orbitals

The name (designation) of hybridized orbitals merely refers to the number and type of

atomic orbitals used in the formation

37
 sp Orbital

Combine one s orbital with one p orbital

Notice the relative shape

difference between bonding
and antibonding lobes

-Allows more overlap!

If the orbitals are subtracted then an identical hybridized orbital is obtained

directed 180 from the first

Bonds formed from the two sp hybridized orbitals will thus have a 180 bond angle

38
 sp2 Hybridization

-Can also hybridize by combining one s orbital with two p orbitals

(would allow formation of three covalent bonds one from each sp2 hybridized)

Look in the x-y plane,

three sp2 hybridized orbitals

pz is coming in and out of the plane

All three sp2 orbitals are in the same plane

(120 apart from one another)

39
 sp3 Hybridization

To form four equivalent bonds carbon can hybridize all of its valence orbitals

(three p and one s to form four sp3 hybrids)

The four sp3 hybridized orbitals have a bond angle of 109.5

Forms a tetrahedral geometry

All bonds can thus have the same bond length and angle,

unlike the model using atomic orbitals

40
 Hybridization Model for Bonding

When a hybridized orbital is used to form a bond with an atom,

a new bonding and antibonding molecular orbital are formed

These bonds have the electron density cylindrically symmetric about the internuclear axis

Bonds that are symmetric about the internuclear axis are called sigma () bonds

Sigma bonds and lone pair of electrons (if they are not involved in resonance)

use hybridized orbitals for the electrons

When 2nd row atoms have the same substituents, they use sp hybridization for two bonding
orbitals, sp2 hybridization for 3 bonding orbitals, and sp3 hybridization for 4 bonding orbitals

Knowing the structure thus allows chemists to predict the hybridization

and also the geometry for the compound

41
 Bonding in Unsymmetrical Compounds

In methane there are 4 identical bonds between carbon and each of the four hydrogens

The carbon atom thus adopts a sp3 hybridization and each H-C-H bond angle is 109.5

for a perfect tetrahedron geometry

When one of the C-H bonds is replaced with a different atom, however,

the perfect tetrahedron geometry is no longer present

(The C-Br bond length is obviously longer than the C-H bonds, thus not a tetrahedron)

We still approximate the carbon as being sp3 hybridized, it is very close as seen by geometry,
but we realize this is an approximation

42
 Variable Hybridization

As seen, the hybridization affects the geometry of a compound

Atomic orbitals need not be hybridized in integer numbers,

need not add exactly one s orbital with 2 p orbitals to yield exactly a sp2 hybridized orbital

As the amount of s and p orbital ratios are changed, the geometry changes

Pure s
sp
sp2
sp3
Pure p

%s
100
50
33
25
0

%p
0
50
67
75
100

Bond <
~
180
120
109.5
90

As %p increases in a hybridized bond, the bond angle decreases

As %s increases in a hybridized bond, the electrons are held closer to the nucleus

(since s orbitals are closer to the nucleus on time average than p orbitals)

The geometry is thus intimately related to the hybridization of the atom

43
 Variable Hybridization

To determine the amount of hybridization for each bond in a nonsymmetrical structure,

first consider how to determine the hybridization for a symmetrical methane

Place carbon at center of box and consider placement of four hydrogens at corners of a box
for an ideal tetrahedron geometry

z

C
y

a

x

Distance for the C-a bond (one of the four hydrogens in methane)

Pa = (x2 + y2 + z2)1/2

44
 Variable Hybridization

Distance for the C-a bond (one of the four hydrogens in methane)

Pa = (x2 + y2 + z2)1/2

C
y
By symmetry x = y = z

Therefore, Pa = (3x2)1/2 = 3 x

a

x
x = Pa / 3

Each composite orbital = (s + x + y + z) = (s + [3/3]Pa)

Typical hybrid orbital therefore = s + Pa

= mixing factor

sp3 = sp(2)

Total s character is i 1/(1 + 2i) = 1

Geometry is also determined as 1 + cosij = 0

= mixing coefficient of bond 1

= mixing coefficient of bond 2

= angle between bonds 1 and 2
45
 Variable Hybridization

Use formula for symmetrical molecule like methane

H
H C
H H

of all four bonds is thus 3

Therefore the H-C-H bond angle can be determined

1 + cosij = 0

1 + (3)(3)cosij = 0

cosij = -1/3

ij = 10928

Pure s
sp
sp2
sp3
Pure p

%s
100
50
33
25
0


0
1
2
3


180
120
109.5
90
46
 Variable Hybridization

What does formula suggest about nonideal tetracoordinate carbon compounds?

H H
H3 C CH3

<C-C-C = 112

(when all four substituents are not the same on a carbon,

the bond angle is not a perfect tetrahedron anymore!)

1 + 2cos(112) = 0

2 = 2.67

The C-C bonds in propane use a sp2.67 hybridized orbital from the central carbon

A molecule can place substituents further apart by using a hybrid orbital with less p character
(greater p character results in smaller angles for bonds)

47
 Variable Hybridization

How to determine the H-C-H bond angle in propane?

The total s character in all four bonds must equal to 1

i 1/(1 + 2i) = 1

Therefore 2/(1 + 2C-C) + 2/(1 + 2C-H) = 1

2 = 2.67 for both C-C bonds

2/(1 + 2.67) + 2/(1 + 2C-H) = 1

if solve for 2C-H, 2 = 3.38 for both C-H bonds

Therefore the H-C-H bond angle in propane can be solved by 1 + (3.38)(3.38)cosH-C-H = 0

H-C-H = 107.4

Factors affecting the ratio of s and p orbitals used to form bond:

1) Electrons in bonds from s orbitals are closer to the nucleus than p orbitals

2) As the percent s character increases in a bond, the bond angle is larger
48
 Variable Hybridization

If the p character is increased in a bond, allows electrons to be closer to other nucleus

Factors:

1) When carbon is bonded to a more electronegative atom,

the other atom prefers more p character so electrons can be closer

2) Sterically the greater the p character, the smaller the angle,

therefore larger atoms prefer larger angles and more s character

Consider the haloform series

HCX3
<X-C-X

HCF3
108.8

The length of the C-X bond also
HCCl3
110.4
matters as a shorter bond length the
HCBr3
110.8
greater the potential steric interactions

HCI3
113.0

49
 Variable Hybridization

What does this variable hybridization model predict for highly strained systems?

Consider cyclopropane

H H

H H
H H

The line angle drawing implies a <C-C-C bond angle of 60

Using atomic orbitals, this angle is too small

(the smallest angle possible is 90 if pure p orbitals were used for the bonds)

More importantly an organic chemist wants to know where the electrons are located for the
bond between the carbons (Valence Bond Theory assumption is that bonds are a result of
sharing electrons between two bonded atoms)

If we know where the electron density is located,

we can understand the properties of these highly strained systems

50
 Variable Hybridization

It has been determined that the <H-C-H bond angle in cyclopropane is 118,

what therefore is the <C-C-C bond angle in this case?

1 + 2C-H cos(118) = 0

2C-H = 2.13

2/(1 + 2.13) + 2/(1 + 2C-C) = 1

C-C bond uses more

2C-C = 4.53

p character in bond

1 + 4.53 cos(C-C) = 0

<C-C-C = 102.8

Model predicts that electron density is not located directly between two carbons

<C-C-C bond angle is 60

C <C-C-C bond angle is 102.8

in line angle drawing
C C using where electrons are located

This is what is referred to as bent bonds

51
 Bent Bond Theory for Bonding

Some argue that this idea of bent bonds should be used instead of the concept of
hybridization in bonding in all organic compounds

Instead of using the idea of and bonds in organic compounds,

the bonding is merely a result of overlap of tetrahedral bonding for a carbon atom

Also instead of using the sp3 hybridization model for a saturated carbon,

rationalize the tetrahedral geometry is a result of placing the electrons

in the four bonds to carbon as far apart as possible

(thus at the corners of a box in a tetrahedral geometry)

This is easy to rationalize for saturated carbons,

as the model relative to hybridization bonding is nearly identical

Bonding occurs by overlapping The bond angles in ethane

orbitals to form new bond
would thus closely match

109.5 in methane

Tetrahedral carbon

with 109.5 bond angles
52
 Bent Bond Theory for Bonding

How would this bent bond theory account for multiple bonds?

(hybridization assumes the formation of bonds to account for multiple bonds)

Instead of sp3 in methane,

H C C H H C C H ethene has a sp2 hybridization
H H H H with p orbitals overlapping for
the second bond

Instead of using sp2 hybridization, bent bond theory would merely align two of the
tetrahedral orbitals toward each other to form the two bonds

Bonds would bend toward

This model would thus also predict each other to allow 2 bonds
that all hydrogens in ethylene between both atoms

would be in the same plane

The <H-C-H angle in ethene would be greater than 109.5 due to the bent bonds being
moved away thus allowing the other two C-H bonds to increase the bond angle

53
 Bent Bond Theory for Bonding

In acetylene therefore three bonds would form between the two carbons

by aligning the three orbitals toward each other

This bent bond theory also allows for the prediction that the C-C bond length

is longest in ethane but decreases in ethene and is shortest in acetylene

Concept of hybridization is still prevalent in

organic chemistry models

(and we will use this description also),

but it is only a model to explain experimental
observations

and not the only model

54
 Bonding Theory in Organic Compounds

Valence Bond Theory: Electrons are located in discrete pairs between specific atoms

Molecular Orbital Theory: Electrons are located in the molecule, not held in discrete regions
between two bonded atoms

Most organic chemists think intuitively about compounds using valence bond theory, we
consider reactions with certain functional groups by considering how the discrete bond reacts

In a particular reaction, a discrete bond breaks and a new bond forms between two atoms

It would be more useful, however, if we could determine where exactly the electrons are
located in a molecule

Are bonds truly a result of sharing of electrons between two atoms (valence bond theory),

or are the electrons shared with the entire molecule (molecular orbital theory)

How can we determine where the electrons are located?

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