Part I Organic Chemistry

Chapter 1 The Nature of the Covalent Bond

Denition of Organic Chemistry

The eld of Organic Chemistry is the chemistry of carbon compounds

Ia

IIa

IIIa

IVa

Va

VIa

VIIa

VIII

Ib

IIb

IIIb

IVb

Vb

VIb

VIIb

1
1

10

11

12

13

14

15

16

17

18
2

1
3

H
1.008
Wasserstoff

He
4.0003
Helium

10

2
11

Li
6.94
Lithium

Be
9.01
Beryllium

B
10.81
Bor

C
12.011
Kohlenstoff

N
14.01
Stickstoff

O
16.00
Sauerstoff

F
19.00
Fluor

Ne
20.18
Neon

12

13

14

15

16

17

18

3
19

Na
22.99
Natrium

Mg
24.31
Magnesium

Al
26.98
Aluminium

Si
28.09
Silicium

P
30.97
Phosphor

S
32.06
Schwefel

Cl
35.45
Chlor

Ar
39.95
Argon

20

21

22

23

24

25

26

27

28

29

30

31

32

33

34

35

36

4
37

K
39.10
Kalium

Ca
40.08
Calcium

Sc
44.96
Scandium

Ti
47.90
Titan

V
50.94
Vanadium

Cr
52.00
Chrom

Mn
54.94
Mangan

Fe
55.85
Eisen

Co
58.93
Cobalt

Ni
58.71
Nickel

Cu
63.55
Kupfer

Zn
65.37
Zink

Ga
69.72
Gallium

Ge
72.59
Germanium

As
74.92
Arsen

Se
78.96
Selen

Br
79.90
Brom

Kr
83.80
Krypton

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

53

54

5
55

Rb
85.47
Rubidium

Sr
87.62
Strontium

Y
88.91
Yttrium

Zr
91.22
Zirconium

Nb
92.91
Niob

Mo
95.94
Molybdn

Tc
98.91
Technecium

Ru
101.07
Ruthenium

Rh
102.91
Rhodium

Pd
106.4
Palladium

Ag
107.87
Silber

Cd
112.40
Cadmium

In
114.82
Indium

Sn
118.69
Zinn

Sb
121.75
Antimon

Te
127.60
Tellur

I
126.90
Iod

Xe
131.30
Xenon

56

57

72

73

74

75

76

77

78

79

80

81

82

83

84

85

86

Cs
132.91
Csium

Ba
137.34
Barium

La
138.91
Lanthan

Hf
178.49
Hafnium

Ta
180.95
Tantal

W
183.85
Wolfram

Re
186.2
Rhenium

Os
190.2
Osmium

Ir
192.22
Iridium

Pt
195.09
Platin

Au
196.97
Gold

Hg
200.59
Quecksilber

Tl
204.37
Thallium

Pb
207.2
Blei

Bi
209.98
Bismut

Po
208.98
Polonium

At
209.99
Astat

Rn
222.02
Radon

87

88

89

104

105

106

107

108

109

Fr
223.02
Francium

Ra
226.03
Radium

Ac
227.03
Actinium

Rf
261.11
Rutherfordium

Db
262.11

Sg
263.12

Bh
262.12

Hs

Mt

Covalent Bond

21

Modications of Carbon

Graphite

Fullerenes

Diamond

thermodynamically stable every carbon has 3 neighbors (but 4 bonds)

metastable every carbon has 3 neighbors (but 4 bonds)

metastable every carbon has 4 neighbors (and 4 bonds)

Covalent Bond

22

Electronic Conguration of Carbon

Orbital 1s
2s 2p 3s 3p 3d

principal QN
1 2 2 3 3 3

azimuthal QN
0 0 1 0 1 2

magnetic QN
0 0 +1, 0, 1 0 +1, 0, 1 +2, +1, 0, 1, 2

spin QN
+, +, +, +, +, +,

combinations
2 2 6 2 6 10

carbon is in the second period and can accommodate a maximum of 8 electrons electronically saturated carbon is always tetravalent 4 bonds; 4 electron pairs; electron octet rule
Covalent Bond 23

Electronic Conguration of Carbon

z z y y x x z y x

E
2px 2py 2pz

2px
2s
z y x

2py

2pz

1s

2s

carbon is in the second period; only 2s and 2p orbitals are relevant for bonding carbon is in the 4 main group and has four electrons electronic conguration of carbon in the ground state is 1s 2s 2p
th 2 2 2
Covalent Bond 24

Hybridization of Atomic Orbitals (by Linear Combination)

3 p

1 s

4
109

109

109

120

120

2 p

1 s

120 180

1 p

1 s

Valence Shell Electron Pair Repulsion (VSEPR) model explains geometries tetrahedral for 4; trigonal planar for 3; and linear for 2 connected atoms or groups
Covalent Bond 25

Hybridization of Atomic Orbitals (by Linear Combination)

2p
2sp
3

2p
2pz 2sp2

2p
2py 2pz

2s
sp3

2s 109
C sp3 sp3 sp3
sp2 C pz

2s 90
sp2 sp2

2sp

90
sp C py sp pz

120

90

1s

1s

1s

Linear Combination of Atomic Orbitals (LCAO) number of orbitals and total energy must remain the same hybridization is an ad hoc explanation to better explain the actually observed geometries
Covalent Bond 26

Formation of Single Bonds (Valence Bond Model)

sp3 1 sp3 C sp3 sp3 2 sp3 C sp3 + sp3 6 H s + sp3 4 H s

H C H

H H H H

H C H HH

methane

H C H H C

H HH C C H H H

ethane

single bonds are -bonds (rotational symmetry) between sp , sp , sp, or s orbitals due to rotational symmetry of the -orbital, rotation is free without breaking the bond
3 2
Covalent Bond 27

Formation of Multiple Bonds

sp2 2 C pz

sp2 + sp2

4 H s H H C C H H

H H C C H H

ethene

sp 2 py C sp pz +

H s

H C C H

ethyne

multiple bonds are -bonds plus -bonds -bonds (no rotational symmetry; node plane along bond) are formed between p orbitals rotation around -bonds requires breaking them (energetically costly)
Covalent Bond 28

Molecular Orbital View of the Covalent Bond (1)

simplied and schematical molecular orbital diagram of the hydrogen molecule

E
1Ht 1Ht
H H

1s(H) 1s(H) * (antibonding)

1s E

1s
H H

1s(H) + 1s(H) (bonding)

molecular orbitals approximated by linear combination of atomic orbitals (LCAO) number and total energy of orbitals must be conserved electron delocalization in bonding orbital leads to stabilization; bond energy antibonding orbital must be destabilized accordingly
Covalent Bond 29

Molecular Orbital View of the Covalent Bond (2)

simplied and schematic molecular orbital diagram of the methane molecule

E
4Ht 1 t
C t
C
3

* 2sp3 1s

2p

2sp 1s(H) * (antibonding)

2s
C
3

2sp + 1s(H) (bonding)

LCAO may involve hybrid orbitals interactions between orbitals of matching symmetry
Covalent Bond 30

Molecular Orbital View of the Covalent Bond (3)

simplied and schematic molecular orbital diagram of the methane molecule

E
4Ht 1 t
C t
C H

* 2p 1s 2s

2s(C) + 2p(C) 1s(H) * (antibonding)

2s(C) + 2p(C) + 1s(H) (bonding)

a more correct approach would start from atomic orbitals instead of hybrid orbitals result will be (almost) the same due to mixing of orbitals VSEPR model and hybridization are useful and valid simplications
Covalent Bond 31

Molecular Orbital View of the Covalent Bond (4)

simplied and schematic molecular orbital diagram of the ethane molecule

E
H3C t * t CH3
C
3

2sp 2sp3 * (antibonding)

2sp3 E

2sp3

2sp3 + 2sp3 (bonding)

LCAO may involve molecular fragments of matching symmetry the simplied diagram above leaves away the molecular orbitals of the CH bonds
Covalent Bond 32

Molecular Orbital View of the Covalent Bond (5)

simplied and schematic molecular orbital diagram of the ethene molecule

E
H2C t * * LUMO 2pz 2sp
2

t CH2

* 2sp2 2sp2
C C

antibonding

E HOMO E

2pz 2sp
2

2pz 2pz
C C

antibonding

2pz + 2pz
C C

bonding

2sp2 + 2sp2

bonding

only orbitals of matching symmetry can mix or interact distinct -bond (from sp ) and -bond (from p ) with dierent bond energies chemistry dominated by highest occupied, lowest unoccupied molecular orbitals (HOMO, LUMO)
2 z
Covalent Bond 33

Molecular Orbital View of the Covalent Bond (6)

simplied and schematic molecular orbital diagram of the ethyne molecule

E
HC t * * LUMO 2py, 2pz 2sp E HOMO E
C C C C

t CH

C
2

* 2sp 2sp2

antibonding

2py, 2pz 2sp

2pz 2pz
C C

2py 2py
C C

antibonding

2pz + 2pz
C C

2py + 2py bonding

bonding

2sp2 + 2sp2

triple bonds are similar in reactivity to double bonds

Covalent Bond 34

Polarization of Covalent Bonds

unpolarized -bond
A A

polarized -bond
A !+ X !
A

ionic bond
X

increasing electronegativity (of X and Y) negative inductive E ect (I e ect)

!" !!" !# !!# !!!" !$" $" $!" $!!"

% !"# &' #"$ *$"( 3 $") #( #"% ./ #"! )#"$ # !"$ "0 #"% ) !"% 1' #") * &"$ 2 !"# + &"% 1 !"% , '"$ )0 &"$ #4 !") ! !"%

H F> C R H +++ H F> C R H +++

> >

H H > > N C R O C CH3 H H H + H H ++ H > Cl C R H ++

>

H > Br C R H + H > F C R H +

F F > > F C R F C R +++ F H ++ F ++ > F C> CH2> CH2 R F +++ +

> >

Covalent Bond

35

A Molecular Orbital Representation of Polarized Bonds

simplied and schematic molecular orbital diagrams of the CC and the CF bond
E
H3C t
C C

t CH3

H3C t
C C F

tF

* 2sp3 E
C C

2sp3

2sp3

EC EF
C C F

2sp3

atomic orbitals (and hybrid orbitals) of more electronegative elements are lower in energy increasing energy dierence between bonding partners implies less orbital overlap bonding/antibonding MO are closer in energy to AO from more/less electronegative element bonding/antibonding MO look more like AO from more/less electronegative element
Covalent Bond 36

Molecules with Several Multiple Bonds

sp2 sp2 H C

cumulated double bonds

H H C C C H H

sp

H 120 H

C pz

! "
py

" !
py

C H

120

1,2-propadiene (a "cumulene")

pz

isolated double bonds

H C H C
H 120 H

sp2

sp2

sp3

sp2

sp2

"
H C C C H H H H H
C C H H H C

"
C H H pz 120 C H

!
pz pz

1,4-pentadiene

!
pz

neither cumulated nor isolated multiple bonds communicate, i.e., interact electronically cumulated or isolated multiple bonds are not conjugated
37

Molecular Orbital Representation of Cumulated Double Bonds

simplied and schematic molecular orbital diagram of 1,2-propadiene

t
C t * * 2py, 2pz 2sp 2py or 2pz 2sp2
C C C C C C C

t CH2 *

C
2

C
2

2sp 2sp

2sp 2sp

antibonding

2pz 2pz
C C

2py 2py
C C C

antibonding

2pz + 2pz
C C

2py + 2py
C C C

bonding

2sp + 2sp2

2sp + 2sp2

bonding

no MO extends over all three carbon atoms the two HOMO and two LUMO look like those of double bonds the double bonds in cumulenes behave like two individual double bonds
Covalent Bond 38

Conjugated Multiple Bonds

sp2 sp2 sp2 sp2

conjugated double bonds

H H H C C H C C H H

"
H 120 H pz C C

(")
H

"
C C H H pz
sp

!
pz

1,3-butadiene conjugated triple bonds

H C C C C H
sp

H pz

!
sp

120

sp

"
H py C pz

"
C pz

(")
C

"

"
C H pz

1,3-butadiyne

! py

!py

pz

!py

alternating multiple (double or triple) and single bonds are called conjugated multiple bonds conjugated multiple bonds interact with each other electronically; electrons are delocalized
Covelent Bond 39

Conjugated Multiple Bonds

simplied and schematic molecular orbital diagram of 1,3-butadiene

E
2 CH2 + 2 CH H2C=CHCHCH2 antibonding antibonding LUMO 2pz bonding HOMO bonding 1 2 nodes 4 3

all MO extend over all four carbon atoms and do not look like double bond MO the HOMO is less stabilized than the HOMO of ethene conjugated double bonds do not behave like two individual double bonds and are more reactive
Covelent Bond 40

Aromaticity Cyclic Conjugated Multiple Bonds in Benzene (and Related Molecules)

two canonical formulae of benzene

H H H H H H H H H H H H
pz H C

(")
H

"
C C

(")
H

! !

!
pz C pz C

! !
H

C pz

!
pz

"

(")

pz

"

molecules with 2n+1 cyclic conjugated double bonds are called aromatic (Hckel rule) all possible double bonds are symmetrically equivalent, indistinguishable aromatic molecules can be represented by canonical formulae (resonance structures)
Covelent Bond 41

Molecular Orbital Representation of Aromatic Molecules

simplied and schematic molecular orbital diagram of benzene

E
6 HC t C6H6 antibonding nodes 4

LUMO

antibonding

2pz HOMO

bonding

bonding

all MO extend over all six carbon atoms and do not look like double bond MO HOMO is better stabilized than and does not look like double bond HOMO aromatic systems are more stable than double bonds and dierent in reactivity
Covelent Bond 42

Resonance Structures of Aromatic Molecules and Conjugated Molecules

benzene

equal major contributions

naphthalene
CH2

equal major contributions

CH2 H C CH2 H C CH2 CH2 CH2 CH2

H2C

H2C H2C

H2C H2C

H2C H2C

C H

C H

butadiene

major contribution

minor contributions (because of formal charges)

resonance structures are a useful formalism to describe electron delocalization, stability

Covalent Bond 43

Resonance Structures to Evaluate Reactivity (Mesomeric Eects)

double bonds to electronegative heteroatoms withdraw conjugated electrons (M eect

R O C R R O C R O ! C R !+ R

O C

O C

H C

O C

O C HC

O C CH

!+ R !+

O ! C !+ R !+

neighboring heteroatoms with free elctron pairs donate to conjugated electrons (+M eect)
O R H C O R O HC R O CH ! R ! O ! !+ R

resonance structures are a useful formalism to evaluate reactivity

Covalent Bond 44