UNIT 1

1.1 Bonding in Organic Compounds

1.1.1 Carbon makes excellent scaffolds: 6 12.01

• Carbon has 6 electrons (1s2 2s2 2p2) C

– 4 valence electrons carbon
– requires 4 more for a full shell (8)
– forms 4 covalent bonds
– mid-range electronegativity
• C-C and C-H bonds are strong and unreactive
• C can bond – to itself
– to metals
– to heteroatoms (atoms other than C or H)
• Geometrically flexible
– forms chains, rings, multiple bonds.
Nitrogen makes 3 bonds (when uncharged) 7 14.01

• Nitrogen has 7 electrons (1s2 2s2 2p3) N

– 5 valence electrons nitrogen
– requires 3 more for a full shell (8)
– forms 3 covalent bonds and has 1 lone pair
– more electronegative than carbon
– lone pairs are available for reaction

Oxygen makes 2 bonds (when uncharged) 7 16.00

• Oxygen has 8 electrons (1s2 2s2 2p4) 0

– 6 valence electrons oxygen
– requires 2 more for a full shell (8)
– forms 2 covalent bonds and has 2 lone pairs
– more electronegative than nitrogen
– lone pairs are less available for reaction
Fluorine makes 1 bond 9 19.00

• Fluorine has 9 electrons (1s2 2s2 2p5) F

– 7 valence electrons fluorine
– requires 1 more for a full shell (8)
– forms 1 covalent bonds and has 3 lone pairs
– very electronegative
– lone pairs are not available for reaction

Hydrogen makes 1 bond 1 1.008

• Hydrogen has 1 electron (1s1) H

– 1 valence electron hydrogen
– requires 1 more for a full shell (2)
– forms 1 covalent bond
– less electronegative than carbon
Practice Question
Using your knowledge of the bonding arrangements of C, N, O, H and
halogens, draw one plausible structure for each of the following
molecular formulae:
CH3Br CH2O C2H4O
 1.2 Drawing Chemical Structures

Ethanol – C2H5OH – C2H6O

expanded H H

structure
H C C O H

H H

CH3CH2OH
condensed
structure
C2H6O
H H
H
C H
H
C O
H
O
H
line structure
1.2.1 Condensed structures

• ‘get rid’ of the bonds by writing each carbon followed by what

is directly attached.
CH3OH

• Connectivity is important.
Maitotoxin
1.2.2 Line Structures
The basic principles are:

1. Lines represent bonds

2. C is the basis of structure so
• Carbon atoms not shown – assumed to be at intersections
and end of lines.
• C-H bonds omitted (hydrogen count assumed from
valence)
• All heteroatoms shown, including hydrogens bound to
heteroatoms.
3. Geometry depends on hybridisation, use realistic bond angles.
Examples:
X
X X
XX X X
X X
XXX X XX
XX
XX X XXXX
X XX X represents
X X
1.2.3 Showing Bonds in 3D

• When you want to show the 3D shape of a molecule:

• Bonds in the plane of the paper:

• Bonds coming towards you:

• Bonds going away from you:

• For example: H

C H
H
H
Practice Problems

• Draw the line structures for:

molecular formula:
Carbon-carbon bond strength – a conundrum

Consider C to C bond strength going from a single to double to

triple bond:
Bond Enthalpy
/kJ mol-1
[single, 2 electrons] C-C 348
(ethane)
[double, 4 electrons] C=C 614
(ethene)
[triple, 6 electrons] CºC 839
(ethyne)

A double bond is stronger than a single bond but not twice as

strong.
The second bond (and third bond) must be weaker than the first!
WHY?
1.3 Hybridisation

Atomic orbitals – a refresher

In free atoms, electrons are in atomic orbitals (AOs).
• Carbon has valence electrons in:
2s orbital 2p orbitals

• Covalent bonds form when atomic orbitals overlap to form

molecular orbitals.
 • This overlap can be good (end on)

Bonds formed by end-on overlap of AOs are called σ-bonds

• Or not so good (side on)

Side-on overlap of AOs gives
π-bonds.

• A single bond is a σ-bond π-bonds are weaker than σ-bonds.

• A double bond is made from one σ-bond and one π-bond

• A triple bond is made from one σ-bond and two π-bonds
This is why double bonds are reactive whereas single bonds are inert!
Methane – a second conundrum

• Methane (CH4) has 4 single C-H bonds.

• AO theory says these arise from overlap of a hydrogen
1s orbital with either the 2s or 2p orbitals of carbon.
• This could be: Linus Pauling
1s with 2s or 1s with 2p

C H
• However, all four bonds in methane are identical. H
H
We explain this observation in terms of hybridisation.
sp3 hybridisation - alkanes
• 2s orbital mixes with all three 2p orbitals
• 1 x s + 3 x p = 4 x sp3
• 4 identical orbitals = 4 σ-bonds
eg methane:
tetrahedral
sp2 hybridisation - alkenes
• 2s orbital mixes with two 2p orbitals
• 1 x s + 2 x p = 3 x sp2 + 1 x p (unhybridised)
• 3 identical orbitals, 1 different = 3 σ-bonds, 1 π-bond
eg ethene:
trigonal
planar
sp hybridisation - alkynes
• 2s orbital mixes with one 2p orbital
• 1 x s + 1 x p = 2 x sp2 + 2 x p (unhybridised)
• 2 identical orbitals, 2 different = 2 σ-bonds, 2 π-bonds
eg ethyne:
linear
Bonding - Summary
C bonded to: geometry hybridisation

four atoms
(by single bonds) tetrahedral
[CH4, CH3CH3, CH3X Ð = 109°
sp3
(X = halogen, OH ....)]
three atoms (trigonal) planar
(two by single bonds Ð = 120°
one by double bond) sp2
[CH2=CH2, H2C=O]
two atoms
(one by single bond
one by triple bond) linear
[HCºCH, CH3CºN] Ð = 180° sp
(two double bonds)
[O=C=O,CH2=C=CH2]
 Practice Questions

σ-bonds _____ _____ _____

π-bonds _____ _____ _____
hybridisation at * _____ _____ _____
geometry at * _________ _________ _________
Summary

• Convert between expanded, condensed and line structures.

• Use sp notation and relate this to geometry.
• Describe bonding in terms of sigma and pi bonds.

• Use knowledge of valence to draw sensible organic molecules.

• Recognise common organic functional groups.
• Classify alcohols and alkyl halides as 1o, 2o or 3o.