Structural Theory

Central Premises
Valency: atoms in organic compounds form a fixed number of bonds

Carbon can form one or more bonds to other carbons

Chapter 1

Chapter 1

Dot Structure

IA

4A 5A 6A 7A www.chemtutor.com/struct.htm

Octet rule

Ar: 1s2 2s2 2p6 3s2 3p6

Chapter 1

The electron configuration of atoms

Ar: 1s2 2s2 2p6 3s2 3p6

K: 1s2 2s2 2p6 3s2 3p6 4s1 K: [Ar] 4s1 K+: 1s2 2s2 2p6 3s2 3p6 = Ar Cl : 1s2 2s2 2p6 3s2 3p5 Cl- : 1s2 2s2 2p6 3s2 3p6 = Ar

Na 1s2 2s2 2p6 3s1

give 1 e- to

Cl 1s2 2s2 2p6 3s2 3p5

(1 e- in outermost shell)

(7 e- in outermost shell)
ionic bonding

Na 1s2 2s2 2p6

Ch. 1 - 7

Cl 1s2 2s2 2p6 3s2 3p6

Ionic Bonds

atoms gain or lose electrons to achieve the electronic

configuration of the nearest noble gas o IONS are formed Lithium helium Fluoride neon

Chapter 1

Ionic Bonds

oppositely charged ions attract and form ionic bonds

strong ionic bond (actually in a crystalline lattice)

between atoms of widely different electronegativities

ELECTRONEGATIVITY

Chapter 1

10

Covalent Bonds
between atoms of similar electronegativity (close to

each other in the periodic table)

Atoms achieve octets by sharing of valence electrons

Lewis structure

Chapter 1

11

Ions, themselves, may contain covalent bonds. Consider, as an example, the ammonium ion

N H

H+

H H N H H

(ammonia) (3 bonds on N)

(ammonium cation) (4 bonds on N with a positive charge on N)

Ch. 1 - 12

EN diff < 0.5

EN diff= 0.5-2

EN Diff > 2

Chapter 1

13

Chapter 1

14

Electronegativity
Electronegativity is the ability of an atom to attract electrons It increases from left to right and from bottom to top in the periodic table (noble gases excluded) Fluorine is the most electronegative atom and can stabilize excess electron density the best

Chapter 1

15

Explaining the patterns in electronegativity

The attraction that a bonding pair of electrons feels for a particular nucleus depends on: 1. the number of protons in the nucleus; 2. the distance from the nucleus; 3. the amount of screening by inner electrons.

Chapter 1

16

ELECTRONEGATIVITY DECREASES AS YOU GO DOWN A GROUP

As the halogen atoms get bigger, any bonding pair gets

further and further away from the halogen nucleus, and so is less strongly attracted towards it. The larger pull from the closer fluorine nucleus is why fluorine is more electronegative than chlorine is. As you go down a group, electronegativity decreases because the bonding pair of electrons is increasingly distant from the attraction of the nucleus.

Chapter 1

17

ELECTRONEGATIVITY I NCREASES ACROSS A PERIOD

Consider sodium at the beginning of period 3 and chlorine at the

end (ignoring the noble gas, argon).

Both have their bonding electrons in the 3-level. The electron pair

is screened from both nuclei by the 1s, 2s and 2p electrons but the chlorine nucleus has 6 more protons in it. Therefore, the electron pair gets dragged towards the chlorine. Electronegativity increases across a period because the number of charges on the nucleus increases.

Atomic numbers: Na: 11 Cl: 17

Chapter 1 18

 Writing Lewis Structures

To construct molecules the atoms are assembled with the correct number

of valence electrons
The number of valence electrons = group number of the atom

Carbon is in group 4A and has 4 valence electrons Hydrogen is in group 1A and has 1 valence electron
If the molecule is an ion, electrons are added or subtracted to give it the

proper charge

The structure is written to satisfy the

octet rule for each atom and to

give the correct charge

If necessary, multiple bonds can be used to satisfy the octet rule for each

atom
Chapter 1 19

General Rules
* Hydrogen is NEVER the central atom * The atom with the LOWEST electronegativity will be the central atom in the molecule or ion. (Element present in the least amount). * Place one pair of electrons between each bonded atoms. . * Place lone pairs of electrons about each atom (except H) to satisfy the octet rule. If electron pairs remain put them on the central atom. * If the central atom is not yet surrounded by four electron pairs, convert one of the pairs of valence electrons available on one of the surrounding atoms to Chapter or more pi bonds. 1 20

 Example
Write the Lewis structure for the chlorate ion (ClO3-) The total number of valence electrons including the electron for the

negative charge is calculated

Three pairs of electrons are used to bond the chlorine to the oxygens

The remaining 20 electrons are added to give each atom an octet

Chapter 1

21

 (1)

Examples Lewis structure of CH3Br Total number of all valence electrons:

Br

4 + 1 x 3 + 7 = 14
Ch. 1 - 22

H C Br

H
H H

: :
Br

:
remaining 6 valence electrons

8 valence electrons
Ch. 1 - 23

 The carbonate ion (CO32-):

C:4 e 3xO: 18 e Charge: 2 e Total: 24 valance e

.O

The organic molecules ethene (C2H4) and ethyne (C2H2)

must also use multiple bonds to satisfy the octet rule for each atom

Chapter 1

24

NO2

N:5 e 2xO: 12 e Charge: 1 e Total: 18 valance e

.. .. :O N ..
-

O:

..

HClO

H:1 e O: 6 e Cl: 7 e Total: 14 valance e

Chapter 1

25

 Exceptions to the Octet Rule

The octet rule applies only to atoms in the second row

of the periodic table (C, O, N, F) which are limited to valence electrons in the 2s and 2p orbitals
In second row elements fewer electrons are possible

Chapter 1

26

 Exceptions to the Octet Rule

In higher rows other orbitals are accessible and more than

8 electrons around an atom are possible

Example: PCl5 , SF6 , SF4

Chapter 1

27

Formal charge
A formal charge is a positive or negative charge on an individual atom The sum of formal charges on individual atoms is the total charge of the

molecule or ion
The formal charge is calculated by subtracting the assigned electrons on

the atom in the molecule from the electrons in the neutral atom
Electrons in bonds are evenly split between the two atoms; one to each

atom
Lone pair electrons belong to the atom itself

Formal Charge

# of valance # bonding electrons in free - electrons/2 atom

Chapter 1

(#nonbonding - electrons

28

 Examples

Ammonium ion (NH4)+

Nitrate ion (NO3)-

Double bond

Chapter 1

29

Chapter 1

30

 A Summary of Formal Charges

Chapter 1

31

H2S
Chapter 1

HCN
32

Resonance

4e- (from C) + 3x6e- (from 3 O) + 2e- = 24 e all bonds are equal in length and the charge is spread equally

over all three oxygens

The real structure is a resonance hybrid or mixture of all three Lewis

structures

Chapter 1

33

O O C 1

becomes

O O C 2 O

becomes O

O C 3 O

Structures 13, although not identical on paper, are equivalent; all of its carbonoxygen bonds are of equal length

Ch. 1 - 34

 curved arrows which show the movement of electrons

all structures differ only in position of electrons

electron density is spread equally among the three

oxygens electrostatic potential map

Chapter 1

35

N=5 valance-3 bonding -2 nonbonded=0 C=4 valance-4 bonding=0

N=5 valance-4 bonding = +1 C=4 valance-3 bonding- 2 nonbonding = -1

17. How to Interpret and Write Structural Formulas

Ch. 1 - 37

17A. Dash Structural Formulas

Atoms joined by single bonds can rotate relatively freely with respect to one another

H C H H

HH C C H

H H O

H H C H C HO C H H H

H C C H HH

H C

H O H

H H Equivalent dash formulas for propyl alcohol

Ch. 1 - 38

 Dot formulas are more cumbersome to draw than dash

formulas and condensed formulas

Lone-pair electrons are often (but not always) drawn in,

especially when they are crucial to the chemistry being discussed

Chapter 1

39

17B. Condensed Structural Formulas

Ch. 1 - 40

17C. Bond-Line Formulas

Ch. 1 - 41

Ch. 1 - 42

 Three-Dimensional Formulas
Bonds that lie in the plane of the paper = simple line Bonds that come forward out of the plane = solid wedge Bonds that go back out of the plane of the paper = dashed wedge

Generally to represent a tetrahedral atom:

Two of the bonds are drawn in the plane of the paper about 109o apart The other two bonds are drawn in the opposite direction to the in- plane bonds but right next to each other

109 in plane

Chapter 1

43

Br H H OH Cl

H Examples of bond-line formulas that include three-dimensional representations

H NH2 HO Br H

An example involving trigonal planar geometry Ch. 1 - 44

An example involving linear geometry

Rules for Resonance:

Individual resonance structures exist only on paper The real molecule is a hybrid (average) of all contributing forms

Only electrons are allowed to move between resonance structures The position of nuclei must remain the same Only electrons in multiple bonds and nonbonding electrons can be moved
All structures must be proper Lewis structures

Chapter 1

45

 The energy of the actual molecule is lower than the energy of any single

contributing form
The lowering of energy is called resonance stabilization

Equivalent resonance forms make equal contributions to the structure of

the real molecule

Structures with equivalent resonance forms tend to be greatly

stabilized

Chapter 1

46

 Unequal resonance structures contribute based on their relative stabilities More stable resonance forms contribute more to the structure of the

real molecule

Chapter 1

47

Rules to Assign Relative Importance of Resonance Form

1. A resonance form with more covalent bonds is more important than

one with less

Example: 6 is more stable and more important because it has more total covalent bonds

Chapter 1

48

2. Resonance forms in which all atoms have a complete valence shell of electrons are more important Example: 10 is more important because all atoms (except hydrogen) have complete octets

Chapter 1

49

3. Resonance forms with separation of charge are less important

Separation of charge cost energy and results in a less stable resonance contributor

less important

4. Forms with negative charge on highly electronegative atoms are

more important
Those with positive charge on less electronegative atoms are also more important
Chapter 1 50

NITRATE ION
All N-O bond lengths are equal the negative charge spread over all three atoms equally three equivalent resonance forms Curved arrows show the movement of electrons between forms

When these forms are hybridized (averaged) the true structure of the nitrate ion is obtained
Most electronegative

Chapter 1

51

Examples

(1) Benzene

(2) Carboxylate ion (RCOO-)

. .O. .

. . O. .
.. . . .O. ..

..

O
. . .O.

(3) Ozone (O3)

Ch. 1 - 52

53

Chapter 1

Quantum Mechanics
A mathematical description of bonding that takes into account the

wave nature of electrons A wave equation is solved to yield a series of wave functions for the atom The wave functions psi (Y) describe a series of states with different energies for each electron Wave Equations are used to calculate: The energy associated with the state of the electron The probability of finding the electron in a particular state

Chapter 1

54

 The phase sign of a wave equation indicates whether

the solution is positive or negative when calculated for a given point in space relative to the nucleus

The sign of the wave function does not indicate a greater or

lesser probability of finding an electron in that location

Chapter 1

55

 Constructive interference occurs when wave functions with the same phase sign interact. There is a reinforcing effect and the amplitude of the wave function increases

Destructive interference occurs when wave functions with opposite phase signs interact. There is a subtractive effect and the amplitude of the wave function goes to zero or changes sign

Ch. 1 - 56

Ch. 1 - 57

 Atomic Orbitals (AOs)

The physical reality of Y is that when squared (Y 2) it gives the

probability of finding an electron in a particular location in space

Plots of Y
2

in three dimensions generate the shape of s, p, d and

f orbitals
Orbital: a region in space where the probability of finding an

electron is large volumes which contain the electron 90-95% of the time

Chapter 1

58

10. Atomic Orbitals and Electron Configuration

The greater the number of nodes in an orbital the higher its energy
Ch. 1 - 59

2s and 2p orbitals each have one node and are higher in energy than the 1s orbital which has no nodes

s orbitals

Chapter 1

60

p Orbitals

Chapter 1

61

d Orbitals

Chapter 1

62

 Atoms can be assigned electronic configuration using

the following rules: 1. Aufbau Principle: The lowest energy orbitals are filled first 2. Pauli Exclusion Principle: A maximum of two spin paired electrons may be placed in each orbital 3. Hunds Rule: One electron is added to each degenerate (equal energy orbital) before a second electron is added

Chapter 1

63

 Molecular Orbitals (MOs)

A simple model of bonding is illustrated by forming molecular H2 from H atoms and varying distance: Region I: The total energy of two isolated atoms Region II: The nucleus of one atom starts attracting the electrons of the other; the energy of the system is lowered Region III: at 0.74 the attraction of electrons and nuclei exactly balances repulsion of the two nuclei; this is the bond length of H2 Region IV: energy of system rises as the repulsion of the two nuclei predominates

Chapter 1

64

An atomic orbital represents the region of space where one or two electrons of an isolated atom are likely to be found

A molecular orbital (MO) represents the region of space where one or two electrons of a molecule are likely to be found

Ch. 1 - 65

An orbital (atomic or molecular) can contain a maximum of two spin-paired electrons (Pauli exclusion principle) When atomic orbitals combine to form molecular orbitals, the number of molecular orbitals that result always equals the number of atomic orbitals that combine

Ch. 1 - 66

A bonding molecular orbital (ymolec) results when two orbitals of the same phase overlap

Ch. 1 - 67

An antibonding molecular orbital (y*molec) results when two orbitals of opposite phase overlap

Ch. 1 - 68

Ch. 1 - 69

Molecular orbitals of H2

Chapter 1

70

sp3 Hybridization
The structure of methane with its four identical tetrahedral bonds cannot

be adequately explained using the electronic configuration of carbon

H H C H (line bond structure)

Hybridization of the valence orbitals (2s and 2p) provides four new

identical orbitals which can be used for the bonding in methane

Orbital hybridization is a mathematical combination of the 2s and 2p

wave functions to obtain wave functions for the new orbitals

Chapter 1 71

Structure of Methane
When one 2s orbital and three 2p orbitals are hybridized four new and

identical sp3 orbitals are obtained Each new orbital has one part s character and 3 parts p character The four identical orbitals are oriented in a tetrahedral arrangements
The four sp3 orbitals are then combined with the 1s orbitals of four

hydrogens to give the molecular orbitals of methane

Each new molecular orbital can accommodate 2 electrons

Chapter 1

72

Hybridization sp3 sp3 hybridized carbon

covalent bond

H H C H H

(line bond structure)

Ch. 1 - 73

Hybridization sp3

H H C H (Lewis structure) H

109o H
Ch. 1 - 74

H C H H

Tetrahedral structure Carbon with 4 bonds

(3-D stucture)

12A. The Structure of Methane

Ch. 1 - 75

Ch. 1 - 76

Ch. 1 - 77

Ch. 1 - 78

Chapter 1

79

 Ethane (C2H6)
The carbon-carbon bond is made from overlap of two sp3 orbitals to form a bond The molecule is approximately tetrahedral around each carbon

Chapter 1

80

 Generally there is relatively free rotation about bonds

Very little energy (13-26 kcal/mol) is required to rotate around the carbon-carbon bond of ethane

Chapter 1

81

sp3 hybridized N

Chapter 1

82

13. The Structure of Ethene (Ethylene): sp2 Hybridization

sp2

~120 H H ~120o C C H H ~120o

1 bond + 1 bond sp2 hybridized carbon

Ch. 1 - 83

sp2

3-Dimensional View -bond (-orbitals overlap) H C H C H H

Planar structure
Ch. 1 - 84

Carbon with (3 + 1) bonds

 The three sp2 hybridized orbitals come from mixing one s and two

p orbitals One p orbital is left unhybridized The sp2 orbitals are arranged in a trigonal planar arrangement The p orbital is perpendicular (orthoganol) to the plane

Chapter 1

85

Ch. 1 - 86

Ch. 1 - 87

Ch. 1 - 88

Ethylene

Chapter 1

89

The orbital is lower in energy than the orbital

The ground state electronic configuration of ethene is shown

Chapter 1

90

 The Structure of Ethene (Ethylene) : sp2 Hybridization

An alkene

The geometry around each carbon is called trigonal planar

All atoms directly connected to each carbon are in a plane The bonds point towards the corners of a regular triangle The bond angle are approximately 120o

Chapter 1

91

 Restricted Rotation and the Double Bond

There is a large energy barrier to rotation

(about 264 kJ/mol)

around the double bond This corresponds to the strength of a bond

The rotational barrier of a carbon-carbon single bond is

13-26

kJ/mol
This rotational barrier results because the p orbitals must be well aligned

for maximum overlap and formation of the bond

Chapter 1

92

13B. CisTrans Isomerism

Stereochemistry of double bonds

H H H
H H3C
i
Ch. 1 - 93

R R identical to H H
H H identical to
i

Pr CH3

Pr

H3C
(trans)

CH3

different from CH3

CH3
(cis)

Restricted rotation of C=C

Ch. 1 - 94

 Cis-Trans System
Useful for 1,2 disubstituted alkenes

e.g. (1) Cl H Br vs. Cl Br H

H trans -1-Bromo2-chloroethane
Ch. 1 - 95

H cis-1-Bromo2-chloroethane

(2)

H vs. H trans -3-Hexene H H cis -3-Hexene

Br Br Br vs. Br Dibromopropene

(3)

Dibromopropene
Ch. 1 - 96

trans -1,3-

cis -1,3-

Orbitals in Boron

Chapter 1

97

14. The Structure of Ethyne (Acetylene): sp Hybridization

sp

1 bond + 2 bond H C 180o Linear structure Carbon with (2 + 2 ) bonds

Ch. 1 - 98

H sp2 hybridized carbon

Ch. 1 - 99

Ch. 1 - 100

Ch. 1 - 101

sp orbital 50% s character, 50% p character sp2 orbital 33% s character, 66% p character sp3 orbital 25% s character, 75% p character

Ch. 1 - 102

 Bond Lengths of Ethyne, Ethene and Ethane The carbon-carbon bond length is shorter as more bonds hold the carbons together With more electron density between the carbons, there is more glue to hold the nuclei of the carbons together The carbon-hydrogen bond lengths also get shorter with more s character of the bond 2s orbitals are held more closely to the nucleus than 2p orbitals A hybridized orbital with more percent s character is held more closely to the nucleus than an orbital with less s character

sp

sp2

sp3

Chapter 1

103

Orbitals in Beryllium

Chapter 1

104

 Molecular Geometry: The Valence Shell Electron Pair

Repulsion (VSEPR) Model

This is a simple theory to predict the geometry of molecules All sets of valence electrons are considered including:
Bonding pairs involved in single or multiple bonds Non-bonding pairs which are unshared

Electron pairs repel each other and tend to be as far apart as

possible from each other

Non-bonding electron pairs tend to repel other electrons more

than bonding pairs do (i.e. they are larger)

The geometry of the molecule is determined by the number of

sets of electrons by using geometrical principles

Chapter 1 105

 Methane

The valence shell of methane contains four pairs

or sets of electrons To be as far apart from each other as possible they adopt a tetrahedral arrangement (bond angle 109.5o)

Chapter 1

106

 Ammonia
When the bonding and nonbonding electrons are considered there are 4

sets of electrons
The molecule is essentially tetrahedral but the actual shape of the bonded

atoms is considered to be trigonal planar

The bond angles are about 107o and not 109.5o because the non-bonding

electrons in effect are larger and compress the nitrogen-hydrogen bond

Chapter 1

107

 Water
There are four sets of electrons including 2 bonding pairs and 2 non-

bonding pairs
geometry is essentially tetrahedral but the actual shape of the atoms

is considered to be an angular arrangement

The bond angle is about 105o because the two larger nonbonding

pairs compress the electrons in the oxygen-hydrogen bonds

Chapter 1

108

 Boron Trifluoride

Three sets of bonding electrons are farthest apart in a trigonal planar arrangement (bond angle 120o)

Chapter 1

109

Beryllium Hydride
Two sets of bonding electrons are farthest apart in a linear arrangement (bond angles 180o)

Ch. 1 - 110

Carbon Dioxide

180

or

O :: C :: O

There are only two sets of electrons around the central carbon and so the molecule is linear (bond angle 180o)

Electrons in multiple bonds are considered as one set of electrons in total

Ch. 1 - 111

 A summary of the results also includes the geometry of

other simple molecules

Chapter 1

112

sp3d and sp3d2 Hybridization

5 e- pairs

6 e- pairs

Chapter 1

113

 Trigonal planar arrangements of atoms can be drawn in 3-dimensions in

the plane of the paper

Bond angles should be approximately 120o These can also be drawn side-on with the central bond in the plane of

the paper, one bond forward and one bond back

Linear arrangements of atoms are always best drawn in the plane of the

paper

Chapter 1

114

 Three-Dimensional Formulas
Bonds that lie in the plane of the paper = simple line Bonds that come forward out of the plane = solid wedge Bonds that go back out of the plane of the paper = dashed wedge

Generally to represent a tetrahedral atom:

Two of the bonds are drawn in the plane of the paper about 109o apart The other two bonds are drawn in the opposite direction to the in- plane bonds but right next to each other

109 in plane

Chapter 1

115

Br H H OH Cl

H Examples of bond-line formulas that include three-dimensional representations

H NH2 HO Br H

An example involving trigonal planar geometry Ch. 1 - 116

An example involving linear geometry

 Isomers

Isomers are different molecules with the same molecular formula Many types of isomers exist Example
Molecular formula C2H6O They have different structures The two compounds differ in the connectivity of their atoms

Chapter 1

117

 Constitutional Isomers
Constitutional isomers are one type of isomer They are different compounds that have the same molecular formula but different connectivity of atoms They often differ in physical properties (e.g. boiling point, melting point, density) and chemical properties

Chapter 1

118

 Three Dimensional Shape of Molecules

It was proposed in 1874 by vant Hoff and le Bel that the four bonds around carbon where not all in a plane but rather in a tetrahedral arrangement i.e. the four C-H bonds point towards the corners of a regular tetrahedron

Chapter 1

119

 Cis-trans isomers
Result of restricted rotation about

double bonds
same connectivity of atoms different arrangement of atoms in

space
Stereoisomers The molecules below do not

superpose on each other

One molecule is designated cis

(groups on same side) and the other

is trans (groups on opposite side)

Cis-trans isomerism is not possible

if one carbon of the double bond has two identical groups

Chapter 1 120