Organic Chemistry

William H. Brown Christopher S. Foote Brent L. Iverson

1-1

Covalent Bonding & Shapes of Molecules

Chapter 1
1-2

Organic Chemistry
The

study of the compounds of carbon Over 10 million compounds have been identified
about 1000 new ones are identified each day!
C

is a small atom

it forms single, double, and triple bonds it is intermediate in electronegativity (2.5) it forms strong bonds with C, H, O, N, and some metals

1-3

Schematic View of an Atom

a small dense nucleus, diameter 10-14 - 10-15 m, which contains positively charged protons and most of the mass of the atom an extranuclear space, diameter 10-10 m, which contains negatively charged electrons

1-4

Electron Configuration of Atoms

Electrons

are confined to regions of space called principle energy levels (shells)

each shell can hold 2n2 electrons (n = 1,2,3,4......)
N u mb er of Relative En ergies Electrons S hell of Electrons S hell Can Hold in Thes e Shells h igh er 4 32 3 18 2 8 1 2 low er

1-5

Electron Configuration of Atoms

Shells

are divided into subshells called orbitals, which are designated by the letters s, p, d, f,........
s (one per shell) p (set of three per shell 2 and higher) d (set of five per shell 3 and higher) .....

S hell 3 2 1

O rb itals Contain ed in Th at S hell 3s , 3p x , 3p y , 3p z, p lu s five 3d orbitals 2s , 2p x , 2p y , 2p z 1s

1-6

Electron Configuration of Atoms

Aufbau

Principle:

orbitals fill in order of increasing energy from lowest energy to highest energy
Pauli

Exclusion Principle:

only two electrons can occupy an orbital and their spins must be paired
Hunds

Rule:

when orbitals of equal energy are available but there are not enough electrons to fill all of them, one electron is added to each orbital before a second electron is added to any one of them

1-7

Electron Configuration of Atoms

The

pairing of electron spins

1-8

Electron Configuration of Atoms

Table

1.3 The Ground-State Electron Configuration of Elements 1-18

1-9

Lewis Dot Structures

Gilbert

N. Lewis Valence shell:

the outermost occupied electron shell of an atom
Valence

electrons:

electrons in the valence shell of an atom; these electrons are used to form chemical bonds and in chemical reactions
Lewis

dot structure:

the symbol of an element represents the nucleus and all inner shell electrons dots represent valence electrons
1-10

Lewis Dot Structures

Table 1.4 Lewis Dot Structures for Elements 1-18

1A H.
.

2A

3A

4A
.

5A

6A

7A
. :F :

8A He :

Li .

Be :

B:
.

N a. M g :

Al:

. . .N : :O: C: . . . . . P : :S : Si : .

:N e :

: : : :

:Cl : :A r :

:
.

1-11

Lewis Model of Bonding

Atoms

bond together so that each atom acquires an electron configuration the same as that of the noble gas nearest it in atomic number
an atom that gains electrons becomes an anion an atom that loses electrons becomes a cation the attraction of anions and cations leads to the formation of ionic solids an atom may share electrons with one or more atoms to complete its valence shell; a chemical bond formed by sharing electrons is called a covalent bond bonds may be partially ionic or partially covalent; these bonds are called polar covalent bonds
1-12

Electronegativity
Electronegativity:

a measure of an atoms attraction for the electrons it shares with another atom in a chemical bond
Pauling

scale

generally increases left to right in a row generally increases bottom to top in a column

1-13

Formation of Ions
A

rough guideline:

ions will form if the difference in electronegativity between interacting atoms is 1.9 or greater example: sodium (EN 0.9) and fluorine (EN 4.0) we use a single-headed (barbed) curved arrow to show the transfer of one electron from Na to F

Na

Na

in forming Na+F-, the single 3s electron from Na is transferred to the partially filled valence shell of F
N a(1s22s 22p 63s1 ) + F(1s 22s2 2p5 ) N a+ (1s2 2s22p 6) + F-(1s2 2s2 2p6 )
1-14

Covalent Bonds
The

simplest covalent bond is that in H2

H H 0 = -435 kJ (-104 kcal)/mol

the single electrons from each atom combine to form an electron pair
+

H-H

the shared pair functions in two ways simultaneously; it is shared by the two atoms and fills the valence shell of each atom
The

number of shared pairs

one shared pair forms a single bond two shared pairs form a double bond three shared pairs form a triple bond
1-15

Polar and Nonpolar Covalent Bonds

Although

all covalent bonds involve sharing of electrons, they differ widely in the degree of sharing We divide covalent bonds into
nonpolar covalent bonds polar covalent bonds
D i fference in El ectron eg ati vity Betw een Bo nded Ato ms Less than 0.5 0.5 to 1.9 Greater than 1.9

Typ e of Bond N on pol ar cov alent Pol ar co valent Io ns f orm

1-16

Polar and Nonpolar Covalent Bonds

an example of a polar covalent bond is that of H-Cl the difference in electronegativity between Cl and H is 3.0 - 2.1 = 0.9 we show polarity by using the symbols d+ and d-, or by using an arrow with the arrowhead pointing toward the negative end and a plus sign on the tail of the arrow at the positive end
d+ dH Cl H Cl

1-17

Polar Covalent Bonds

Bond

dipole moment (m):

a measure of the polarity of a covalent bond the product of the charge on either atom of a polar bond times the distance between the nuclei Table 1.7 shows average bond dipole moments of selected covalent bonds
Bond Dipole Bond (D ) Bond Dipole Bond (D ) Bond D ipole Bond (D)

H-C H-N H-O H-S

0.3 1.3 1.5 0.7

C-F C-Cl C-Br C-I

1.4 1.5 1.4 1.2

C-O C=O C-N -C=N

0.7 2.3 0.2 3.5

1-18

Lewis Structures
To

write a Lewis structure

determine the number of valence electrons determine the arrangement of atoms connect the atoms by single bonds arrange the remaining electrons so that each atom has a complete valence shell show a bonding pair of electrons as a single line show a nonbonding pair of electrons as a pair of dots in a single bond atoms share one pair of electrons, in a double bond they share two pairs of electrons, and in a triple bond they share three pairs of electrons

1-19

Lewis Structures - Table 1.3

H-O-H H 2 O (8) Water H C C H H C2 H 4 (12) Ethylene H H-C C-H C2H 2 (10) Acetylen e H-N-H H N H 3 (8) Ammonia H H-C-H H CH 4 (8) Meth ane H C O H CH 2O (12) Formald ehyde H O H-Cl HCl (8) Hyd rogen ch loride O C O H

H 2CO 3 (24) Carbonic acid

In

neutral molecules
hydrogen has one bond carbon has 4 bonds and no lone pairs nitrogen has 3 bonds and 1 lone pair oxygen has 2 bonds and 2 lone pairs halogens have 1 bond and 3 lone pairs

1-20

Formal Charge
Formal

charge: the charge on an atom in a molecule or a polyatomic ion To derive formal charge
1. write a correct Lewis structure for the molecule or ion 2. assign each atom all its unshared (nonbonding) electrons and one-half its shared (bonding) electrons 3. compare this number with the number of valence electrons in the neutral, unbonded atom
N umber of = valence electrons in th e neutral, un bonded atom All One h alf of un shared + all sh ared electrons electrons
1-21

Formal charge

Formal Charge

Example: Draw Lewis structures, and show which atom in each bears the formal charge
(a) NH2 + (d) CH3 NH3 (b) HCO3 (e) HCOO

(c) CO3

2-

(f) CH3 COO

1-22

Exceptions to the Octet Rule

Molecules

containing atoms of Group 3A elements, particularly boron and aluminum

: F: :F : : B :F: :

6 electrons in the valence shells of boron and aluminum

Boron trifluoride

: Cl : : Cl : : Al : Cl : :

Aluminum chloride

1-23

Exceptions to the Octet Rule

Atoms

of third-period elements have 3d orbitals and may expand their valence shells to contain more than 8 electrons
phosphorus may have up to 10
: Cl :

:
:O: : Cl

: : : :

: : : :

CH3 -P- CH3 CH3 Trimethylphos phine

Cl :

H- O-P- O-H

: :

: :

: Cl

Cl :

O-H

Phos phoru s pentach loride

Phos phoric acid

1-24

Exceptions to the Octet Rule

sulfur, another third-period element, forms compounds in which its valence shell contains 8, 10, or 12 electrons
: O: : O:

H-S- H
Hydroge n sulfide
:

CH 3 -S-CH 3
Dimethyl sulfox ide
:

H-O- S-O-H
Sulfuric acid
: :
:O :

1-25

Functional Groups
Functional

group: an atom or group of atoms within a molecule that shows a characteristic set of physical and chemical properties Functional groups are important for three reason; they are
1. the units by which we divide organic compounds into classes 2. the sites of characteristic chemical reactions 3. the basis for naming organic compounds

1-26

Alcohols
contain
-C-O-H Fu nctional group
: :

an -OH (hydroxyl) group

H H H-C-C-O-H H H Ethan ol (an alcohol)

Ethanol

may also be written as a condensed structural formula

CH3 -CH2 -OH or CH3 CH2 OH

1-27

Alcohols
alcohols are classified as primary (1), secondary (2), or tertiary (3) depending on the number of carbon atoms bonded to the carbon bearing the -OH group
CH3 CH3 -C-OH CH3 A 1 alcohol H CH 3 -C-OH CH3 A 2 alcohol CH 3 CH3 -C-OH CH 3 A 3 alcoh ol

1-28

Alcohols
there are two alcohols with molecular formula C3H8O
HHH H-C-C-C-O-H H HH H HOH H C-C-C-H HH H or CH3 CH2 CH2 OH a 1 alcohol

or

OH CH3 CHCH3 a 2 alcohol

1-29

Amines
contain

an amino group; an sp3-hybridized nitrogen bonded to one, two, or three carbon atoms
an amine may by 1, 2, or 3
:

CH 3 N H H
Methylamine (a 1 amine)

CH 3 N H CH 3
Dimethylamine (a 2 amine)

CH 3 N CH 3 CH 3
Trimethylamine (a 3 amine)

1-30

Aldehydes and Ketones

contain

a carbonyl (C=O) group

O C Fu nctional group O CH 3 -C-CH3 Aceton e (a ketone)

O O C H CH 3 -C-H Fu nctional A cetaldeh yd e group (an aldehyde)

1-31

Carboxylic Acids
contain
O C O H Fu nctional group

a carboxyl (-COOH) group

:O: CH3 -C-O-H

Acetic aci d (a carboxy li c acid )

or CH3 COOH or CH3 CO2 H

1-32

Carboxylic Esters
Ester:

a derivative of a carboxylic acid in which the carboxyl hydrogen is replaced by a carbon group
O C O Fun ctional group : O: CH3 -C-O-CH2 -CH3

Ethyl acetate (an ester)

: :
1-33

Carboxylic Amide
Carboxylic

amide, commonly referred to as an amide: a derivative of a carboxylic acid in which the -OH of the -COOH group is replaced by an amine
O C N Fu nctional group O CH3 -C-N-H H Acetamid e (a 1 amid e)

the six atoms of the amide functional group lie in a plane with bond angles of approximately 120

1-34

VSEPR
Based

on the twin concepts that

atoms are surrounded by regions of electron density regions of electron density repel each other
H 4 region s of e - d ensity (tetrahed ral, 109.5) 3 region s of e - d ensity (trigon al planar, 120) 2 region s of e - d ensity (lin ear, 180)

:
N

C H H C H

H H H H C H H H

H H

H H

H H

: :

O H

: :

:
O H C C H H C N
1-35

O C

VSEPR Model

Example: predict all bond angles for these molecules and ions
( a ) N H4 + ( e ) CH 3 CH = CH 2 ( h) CH3 CH O ( b ) CH 3 NH 2 ( f ) H 2 CO 3 ( i) CH 3 COOH ( d ) CH 3 OH ( g ) HCO 3 ( j ) BF4 -

1-36

Polar and Nonpolar Molecules

To

determine if a molecule is polar, we need to determine

if the molecule has polar bonds the arrangement of these bonds in space

Molecular

dipole moment (m): the vector sum of the individual bond dipole moments in a molecule
reported in debyes (D)

1-37

Polar and Nonpolar Molecules

these

molecules have polar bonds, but each has a zero dipole moment

F O C O F
Carbon dioxide m =0D Boron trifluoride m=0D

Cl B F Cl Cl C Cl

Carbon tetrachloride m=0D

1-38

Polar and Nonpolar Molecules

these

molecules have polar bonds and are polar molecules

direction of dip ole moment O H H H H Ammonia m = 1.47D N H direction of dip ole moment

Water m = 1.85D

1-39

Polar and Nonpolar Molecules

formaldehyde has polar bonds and is a polar molecule
direction of dip ole moment O C

Formaldehyde m = 2.33 D

1-40

Resonance
For

many molecules and ions, no single Lewis structure provides a truly accurate representation
O H3 C C O Ethan oate ion (acetate ion) and H3 C C O O -

1-41

Resonance
Linus

Pauling - 1930s

many molecules and ions are best described by writing two or more Lewis structures individual Lewis structures are called contributing structures connect individual contributing structures by doubleheaded (resonance) arrows the molecule or ion is a hybrid of the various contributing structures

1-42

Resonance

Examples: equivalent contributing structures

:
:

:O: :N O: :N

N itrite ion (equivalent con trib uting s tru ctures)

O: CH3 :O :C

: O :CH3 O: C

O: : O :-

A cetate ion (equ ivalen t contributin g s tru ctures)

1-43

Resonance
Curved

arrow: a symbol used to show the redistribution of valence electrons In using curved arrows, there are only two allowed types of electron redistribution:
from a bond to an adjacent atom from an atom to an adjacent bond
Electron

pushing is a survival skill in organic chemistry

learn it well!

1-44

Resonance
All

contributing structures must

1. have the same number of valence electrons 2. obey the rules of covalent bonding no more than 2 electrons in the valence shell of H no more than 8 electrons in the valence shell of a 2nd period element 3rd period elements, such as P and S, may have up to 12 electrons in their valence shells 3. differ only in distribution of valence electrons; the position of all nuclei must be the same 4. have the same number of paired and unpaired electrons

1-45

Resonance
The

carbonate ion, for example

a hybrid of three equivalent contributing structures the negative charge is distributed equally among the three oxygens

1-46

Resonance
Preference

1: filled valence shells

structures in which all atoms have filled valence shells contribute more than those with one or more unfilled valence shells
+ CH 3 O

CH 3 O

+ C

H Greater contribution; both carbon and oxygen have complete valence shells

H Lesser contribution; carbon has only 6 electrons in its valence shell

1-47

Resonance
Preference

2: maximum number of covalent

bonds
structures with a greater number of covalent bonds contribute more than those with fewer covalent bonds
CH3 + O

CH3 O

+ C

H Greater contribution (8 covalent bonds )

H Less er contribution (7 covalent bonds )

1-48

Resonance
Preference

3: least separation of unlike charge

structures with separation of unlike charges contribute less than those with no charge separation
O: CH3 - C- CH3
Greater contribution (no separation of unlike charges)
: :O: -

CH3 - C- CH3 Lesser contribution (separation of unlike charges)

1-49

Resonance
Preference

4: negative charge on the more electronegative atom

structures that carry a negative charge on the more electronegative atom contribute more than those with the negative charge on the less electronegative atom
O C (1) CH3 H3 C O C CH3 (b) Greater contribu tion (2) H3 C O C CH3 (c) S hould n ot be d rawn

H3 C

(a) Less er con trib ution

1-50

Quantum or Wave Mechanics

Albert Einstein: E = hn (energy is quantized) light has particle properties Louis deBroglie: wave/particle duality
h mn

Erwin Schrdinger: wave equation wave function, : a solution to a set of equations that depicts the energy of an electron in an atom each wave function is associated with a unique set of quantum numbers each wave function occupies three-dimensional space and is called an orbital 2 is the probability of finding an electron at a given point in space
1-51

Shapes of 1s and 2s Orbitals

Probability

distribution (2) for 1s and 2s orbitals showing an arbitrary boundary surface containing about 95% of the electron density

1-52

Shapes of a Set of 2p Atomic Orbitals

Three-dimensional

shapes of 2p atomic orbitals

1-53

Molecular Orbital Theory

Electrons

in atoms exist in atomic orbitals Electrons in molecules exist in molecular orbitals (MOs) Using the Schrdinger equation, we can calculate the shapes and energies of MOs

1-54

Molecular Orbital Theory

Rules:

combination of n atomic orbitals (mathematically adding and subtracting wave functions) gives n MOs (new wave functions) MOs are arranged in order of increasing energy MO filling is governed by the same rules as for atomic orbitals: Aufbau principle: fill beginning with LUMO Pauli exclusion principle: no more than 2e- in a MO Hunds rule: when two or more MOs of equivalent energy are available, add 1e- to each before filling any one of them with 2e1-55

Molecular Orbital Theory

Terminology

ground state = lowest energy state excited state = NOT lowest energy state = sigma bonding MO * = sigma antibonding MO = pi bonding MO * = pi antibonding MO HOMO = highest occupied MO LUMO = lowest unoccupied MO

1-56

Molecular Orbital Theory

Sigma

1s bonding and antibonding MOs

1-57

Molecular Orbital Theory

MO energy diagram for H2: (a) ground state and (b) lowest excited state

1-58

Molecular Orbitals
computed sigma bonding and antibonding MOs for H2

1-59

Molecular Orbitals
pi

bonding and antibonding MOs

1-60

Molecular Orbitals
computed pi bonding and antibonding MOs for ethylene

1-61

Molecular Orbitals
computed pi bonding and antibonding orbitals for formaldehyde

1-62

Hybrid Orbitals
The

Problem:

bonding by 2s and 2p atomic orbitals would give bond angles of approximately 90 instead we observe bond angles of approximately 109.5, 120, and 180
A

Solution

hybridization of atomic orbitals 2nd row elements use sp3, sp2, and sp hybrid orbitals for bonding

1-63

Hybrid Orbitals
Hybridization

of orbitals (L. Pauling)

the combination of two or more atomic orbitals forms a new set of atomic orbitals, called hybrid orbitals
We

deal with three types of hybrid orbitals

sp3 (one s orbital + three p orbitals) sp2 (one s orbital + two p orbitals) sp (one s orbital + one p orbital)
Overlap

of hybrid orbitals can form two types of bonds depending on the geometry of overlap
bonds are formed by direct overlap bonds are formed by parallel overlap
1-64

sp3 Hybrid Orbitals

each sp3 hybrid orbital has two lobes of unequal size the sign of the wave function is positive in one lobe, negative in the other, and zero at the nucleus the four sp3 hybrid orbitals are directed toward the corners of a regular tetrahedron at angles of 109.5
1-65

sp3 Hybrid Orbitals

orbital overlap pictures of methane, ammonia, and water

1-66

sp2 Hybrid Orbitals

the axes of the three sp2 hybrid orbitals lie in a plane and are directed toward the corners of an equilateral triangle the unhybridized 2p orbital lies perpendicular to the plane of the three hybrid orbitals

1-67

Bonding in Ethylene

1-68

Bonding in Formaldehyde

1-69

sp Hybrid Orbitals
two lobes of unequal size at an angle of 180 the unhybridized 2p orbitals are perpendicular to each other and to the line created by the axes of the two sp hybrid orbitals

1-70

Bonding in Acetylene, C2H2

1-71

Hybrid Orbitals
Group s Orb ital Predicted Bond ed Hyb rid Bond to Carb on ization A ngles 4 sp 3 109.5 Types of Bond s to Carbon 4 sigma b on ds

Examp le HH H-C-C-H HH

N ame Ethan e

sp

120

3 sigma b on ds and 1 p i bond 2 sigma b on ds and 2 p i bonds

H C H C

H Eth ylen e H Acetylene

sp

180

H-C C-H

1-72

Bond Lengths and Bond Strengths

N ame

Formula HH H-C-C-H HH H H C C H H

Bond C-C C-H

Orb ital Overlap

Bond Length (pm)

Bon d Strength [k J (k cal)/mol]

sp 3 -sp 3 sp 3 -1s sp 2-sp 2, 2p-2p sp 2-1s sp-sp, tw o 2p -2p sp-1s

153.2 111.4 133.9 110.0 121.2 109.0

376 (90) 422 (101) 727 (174) 464(111) 966 (231) 556 (133)

Ethan e

Ethylene

C-C C-H C-C C-H

Acetylene H-C C-H

1-73

Covalent Bonds & Shapes of Molecules

End Chapter 1
1-74