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2 Bonding PDF
2 Bonding PDF
The region of space where electrons are held are called orbitals
The property and shape of orbitals is dependent on what shell the electrons are held
A wave function is simply a mathematical formula that describes the region of space the
electron may reside in a given atomic orbital
Atomic s orbital:
In two-dimensions
in three-dimensions
•
Atomic p orbital:
In two-dimensions
in three-dimensions
electron
density
+
- distance
nucleus
Important points:
Density is zero at nucleus
Lobes on opposite sides of the nucleus are out of phase
(different sign)
Combination of Two Waves
As atomic orbitals combine they form a new molecular orbitals that allow electrons to be
shared between the two nuclei
Bond Formation
Only orbitals of like phase can combine in a constructive manner to form a bonding region
where the electrons can reside
Always get the same number of molecular orbitals as atomic orbitals used
Can add and substract two atomic p orbitals to obtain a bonding and antibonding σ bond
p bond
Electron density is not symmetric about the internuclear axis
If bonds formed only from atomic s or p orbitals then the bond angles would always be 90˚
Also could not fill atoms’ valence shell with covalent bonds
Consider carbon
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
The name (designation) of hybridized orbitals merely refers to the number and type of
atomic orbitals used in the formation
sp Orbital
The two hybridized sp orbitals form σ bonds with the other carbon and a hydrogen,
The remaining p orbitals form two additional π bonds
to form a total of three bonds between carbon
sp2 Hybridization
To form four equivalent bonds carbon can hybridize all of its valence orbitals
(three p and one s to form four sp3 hybrids)
Organic chemists use a wedge and dash line system to designate stereochemistry
H
H
H
Bond Rotation
Bonding between two atoms is a result of the overlap of the orbitals from each atom
If only a σ bond is formed between two atoms, then the bond can be
rotated a full 360˚ and maintain the same overlap of the orbitals
Causes substituents to have different relative placement depending upon bond rotation
Rigidity of π Bonds
If π bonds would rotate the bond would lose overlap and hence the bond would be broken
Cis versus Trans
The rigidity of a π bond causes different compounds to be formed that cannot rotate to
interconvert (hence they have different physical properties)
If substituents are on the same side of the double bond, it is called a cis compound
If substituents are on opposite sides of the double bond, it is called a trans compound
Isomers
The cis and trans compounds are one type of relationship that are called isomers
Isomers are any two compounds that are different but have the same molecular formula
Multiple bonds are formed with one σ bond and additional π bonds
lone pair of electrons often go into hybridized orbitals
Resonates
Cannot resonate
sp2 hybridization
sp3 hybridization
How to determine molecular structure
Determine number of lone pair of electrons on an atom that are not involved in resonance
The addition of the above two numbers equals the number of hybridized orbitals required
If the lone pair is resonating with the carbonyl then the N atom is sp2 hybridized,
If the lone pair is not resonating then the N atom is sp3 hybridized
Infrared (IR) spectroscopy (chapter 12) – can measure energy required to cause a bond
vibration, energy of carbonyl stretch is low compared to other carbonyls not in resonance
Nuclear Magnetic Resonance (NMR – chapter 13) – can measure electronic environment around
a nucleus, observe two distinct environments for CH3 groups – thus cannot rotate freely
X-ray – can measure atomic positions, amide structures display nearly 120˚ bond angles for
C-N-C bond angles while this angle is close to 109.5˚ for C-N-C bond angle in amines
Acidity – can measure how easy it is to protonate a nitrogen in an amide versus a nitrogen in
a nonresonating amine, much harder to protonate amide lone pair due to resonance