Chapter 3

Simple Bonding Theory

This chapter presents elementary description of
molecules based on Lewis dot structures, valence
shell electron pair repulsion (VSEPR), and related
topics.

More complete description will be taught with

molecular orbital descriptions at Chapter 5
3.1. Lewis Electron-Dot Diagram
Lewis electron-dot diagrams
- oversimplified
- but a good starting point for analyzing the bonding in molecules

Bonds between two atoms

- when they share one or more pairs of e’s.
Some molecules - nonbonding pairs (lone pairs) of e’s on atoms.

Octet Rule
8 valence e’s (corresponding to s & p e’s outside the noble gas core)
→ form a particularly stable arrangement,
(← noble gases: s2p6 configurations, cf. H: 2 valence e’s).
How to Draw the Lewis electron-dot diagrams
ex. CO2
1. Count the total valance electrons for the molecule. 4 (C) + 6x2 (O) = 16

2. Figure out how many octet electrons the 3 x 8 = 24

molecule should have: 8 electron for each atom
except hydrogen (H is 2).
3. Subtract the valance electrons from octet electrons. 24 – 16 = 8
=> Number of bonding electrons.
4. Divide the number of bonding electrons by two. 8/2 = 4
=> Number of bonds.
5. Draw arrangement of the atoms for the molecule O=C=O
that contains the number of bonds.
The least electronegative atom goes to center
H and halogen bond once.
The chalcogen bond once.
The nitrogen family bond three times, so does boron.
The carbon family bond times. .. ..
6. Find the number of lone pair electrons by subtracting O
.. =C=O
..
the bonding electrons from the valance electrons. Arrange
these around the atoms, until all of them satisfy octet rule.
3.1.1. Resonance
CO32- - 3 drawings (resonance structures) are needed.

Experimental evidence → all the C–O bonds are identical (129 pm)
cf. normal double-bond (116 pm), single-bond (143 pm)

Resonance
A combination of all three, not an equilibrium between them.

CO32-, NO3-, & SO3 - isoelectronic (same electronic structure).

→ same Lewis diagrams

Several resonance structures

→ overall electronic E is lowered (more stable)
→ electronic E levels of the bonding e’s are lowered when the e’s can
occupy a larger space (particle in a large box)
3.1.2. Expanded Shells
When impossible to draw a structure consistent with the octet rule,
→ necessary to increase the # of e’s around the central atom.

Need to use d orbitals for this expansion

→limited to elements of the third & higher periods

ex. ClF3 10 e’s; SF6 12 e’s

IF7 - 14e’s; [TaF8]3- - 16 e’s; [XeF8]2- - 18 e’s

Typically up to 18 electrons!
3.1.2. Expanded Shells
3.1.2. Expanded Shells
However, recent calculations indicate that because the 3d orbitals are so much
higher in energy than the 3s & 3p orbitals for a given atom it is not feasible to
use them. Hyperconjugation might be another explanation.

Hyperconjugation – covalent & ionic bonds

3.1.3. Formal Charge

• Used to help in the assessment of resonance structures & molecular

topology.

• Remember that formal charge is only a tool for assessing Lewis

structures, not a measure of any actual charge on the atoms.

Favored structure
- Minimizing formal charges
- (-) formal charge on more electronegative elements
- Smaller charge separations
 3.1.3. Formal Charge
Examples 1: [SCN]-
Structure A
- only one (-) formal charge on the N atom (the
most electronegative atom in the ion) → fits the
rules well.

Structure B
- a single (-) charge on the S (less electronegative
than N).

Structure C
- charges of 2- on N & 1+ on S
- consistent w/ the relative electronegativities of
the atoms but w/ a larger charge & greater charge
separation than the first.

→ Structure A is most important, structure B is next in importance, &

any contribution from C is minor.
 3.1.3. Formal Charge
Examples 1: [SCN]-
Contribution for real structure:

>
 3.1.3. Formal Charge
Examples 2: [CNO]-
Electronegativities: C<N<O

The most stable

H+ + [CNO]- HCNO
X CNOH
 3.1.3. Formal Charge
Better structures with expanded shells: minimized formal charge
 3.1.4. Multiple Bonds in Be and B Compounds
A few molecules, such as BeF2, BeCl2, & BF3, seem to require multiple
bonds to satisfy the octet rule for Be& B, even though we do not usually
expect multiple bonds for fluorine & chlorine.

Structures minimizing formal charges for these molecules

- Four e’s in the valence shell of Be
- six e’s in the valence shell of B
→ in both cases less than the usual octet.

Alternatively, multiple bonds, w/ BeF2 analogous to CO2

& BF3 analogous to SO3.

1+ 2- 1+ 1+ 2- 1+ 1+
1-

1. While B or Be have negative formal charge, F or Cl have positive

formal charge!
2. The unusual multiple bonds for F and Cl
3.1.4. Multiple Bonds in Be and B Compounds
In the solid, a complex network is formed w/ C. N. 4 for the Be atom.

.. ..
..Cl-Be-Cl ..
.. ..
High Temp.

The monomeric structure: Unstable

In the dimer & polymer, the halogen atoms share lone pairs w/ the Be
atom & bring it closer to the octet structure.

The monomer is still frequently drawn as a singly bonded structure w/

only four e’s around the Be & the ability to accept more from lone pairs
of other molecules (Lewis acid behavior, discussed in Chapter 6).
 3.1.4. Multiple Bonds in Be and B Compounds

Bond lengths in all the boron trihalides: 131pm

- shorter than expected for single bonds (152pm),
→ partial double bond character seems reasonable
- Molecular orbital calculations support significant double bond character.

On the other hand, they combine readily w/ other molecules that can
contribute a lone pair of e’s (Lewis bases), forming a roughly tetrahedral
structure w/ four bonds:
3.2. Valence Shell Electron Pair Repulsion Theory
Valence Shell Electron Pair Repulsion Theory (VSEPR)
It provides a method for predicting the shape of molecules, based on the electron
pair electrostatic repulsion.

Limitation:
Approximate shapes for molecules, not a complete picture of bonding.

Geometry Determination:
Valence e pairs position themselves as far from each other as possible.

AXmEn
A = central atom, X = Ligands, & E = a lone pair of e’s.

Steric Number (SN = m + n)

The # of positions occupied by atoms or lone pairs around a central
atom; - lone pairs & bonds: nearly equal in their influence on
molecular shape.
3.2. Valence Shell Electron Pair Repulsion Theory
3.2. Valence Shell Electron Pair Repulsion Theory
For SN = 8 :
Regular Square Antiprism Structure
- a cube w/ the top & bottom faces twisted 45° into the antiprism
arrangement.

[TaF8]3-
- Distorted square antiprism symmetry
 3.2.1. The Lone Pair Repulsion
Steric Number = 4
The effect of lone pairs on molecular shape

a trigonal pyramid w/ the 3 bonding pairs; w/ the lone

pair, - a nearly Td shape.

2 lone pairs & 2 bonding pairs - repel each other.

(lp-bp) repulsion > (bp-bp) repulsion

- the H-O-H bond angle is only 104.5°

Predict approximate molecular shapes

- lone pairs are able to spread out & occupy more space.
3.2.1. The Lone Pair Repulsion
Steric number = 5

trigonal bipyramidal (tbp) geometry

- two possible locations of lone pairs: axial & equatorial.

If there is a single lone pair (e.g., SF4)

- the lone pair occupies an equatorial position.

distorted structure by the lone pair

← it spreads out in space & effectively squeezes the
rest of the molecule together.
3.2.1. The Lone Pair Repulsion
ClF3 90° lp-lp interaction

Repulsive Effects

lp-lp interactions > lp-bp interactions > bp-bp interactions

Interactions at angles of 90° or less are most important

(larger angles generally have less influence)
A vs C
The lp-bp angles are more important;
C (only four 90° lp-bp) is favored over A (six 90° lp-bp).
3.2.1. The Lone Pair Repulsion
• Double & Triple bonds
- slightly greater repulsive effects than single bonds because of the
repulsive effect of π electrons.

- Same positions as lone pairs.

- Double bonds to O in SOF4, ClO2F3, & XeO3F2: all equatorial

- Multiple bonds: tend to occupy more space than single bonds

→ cause distortions → squeeze the rest of the molecule together.
- Molecules having both lone pairs & multiple bonds,
→ may compete for space.
3.2.3. Electronegativity and Atomic Size Effects
Electronegativity
– The use of formal charge arguments.
– Determining the arrangement of outer atoms around a central atom
– Influencing bond angles
– The effects of electronegativity & atomic size frequently parallel each other,
but in the few cases in which they have opposite effects, electronegativity
seems to prevail.

25
 3.2.3. Electronegativity and Atomic Size Effects
Electronegativity scales
- Linus Pauling (1930s) - a means of describing bond energies.
- Bond E of polar bonds (atoms w/ different electronegativities) are larger than
the average of the bond E of the two homonuclear species.
i.e., Bond E (kJ/mol)
HCl (428) > calc (336) = [H2 (432) + Cl2 (240)] / 2.
- From data like these, Pauling calculated electronegativity values
→ could be used to predict other bond E.
- More recent values
- from other molecular & atomic properties, such as IE & EA.
 3.2.3. Electronegativity and Atomic Size Effects
Different methods,
but will give the same results in qualitative arguments.

- F: the largest electronegativity (exception He & Ne; no known stable compd)

- Electronegativity decreases toward the lower left corner of the periodic table.

- Electronegativities of noble gases – calculated easily from IE’s (than from BE)
The noble gases have higher IE’s than the halogens
The noble gas atoms are smaller than the neighboring halogen atoms
(Ne < F due to a greater Z* of Ne)
- The greater Z* attract e’s strongly to the nucleus
→ strong attraction on e’s of neighboring atoms
→ high electronegativities for the noble gases
 3.2.3. Electronegativity and Atomic Size Effects
Electronegativity and bond angles
Bond Angles – explained by electronegativity or size arguments

• Molecules having a large difference in electronegativities between the central & outer
atoms → smaller bond angles.
- Larger electronegativity → drawing e’s to itself & away from the central atom
→ reducing the repulsive effect of those bonding e’s.
- F containing compds → smaller angles than Cl containing compds
→ smaller angles than Br or I containing compds.

• Size effects: as the size of the outer atom increases in F < Cl < Br < I, the angle increases.
•
3.2.3. Electronegativity and Atomic Size Effects

PF3 97.8
PCl3 100.3
PBr3 101.0
OSF2 92.3
OSCl2 96.2
OSBr2 98.2
3.2.3. Electronegativity and Atomic Size Effects
For the molecules containing H, neither the electronegativity nor the size argument
works well.

NH3
- should have the largest angle in the series of N compds based on the
electronegativity argument & the smallest angle based on the size argument;
- instead, it has nearly the same angle as NCl3.

Similar problems are found for H2O, H2S, PH3, AsH3, & SbH3.
The two effects seem to counterbalance each other, resulting in the intermediate
angles.
3.2.3. Electronegativity and Atomic Size Effects
Outer atoms remain the same but the central atom is changed.
The H series & the Cl series in Table 3-5.

As the central atom becomes more electronegative,

→ it pulls e’s in bonding pairs more strongly toward itself.
→ increases the concentration of bonding pair e’s near the central atom,
→ causing the bonding pairs to repel each other more strongly,
→ increasing the bond angles.

→The compound w/ the most electronegative central atom has the largest bond angle.
3.2.3. Electronegativity and Atomic Size Effects
The size of the central atom

When the central atom is larger,

→ all the e pairs are naturally at greater distances from each other.

The effect is greater for the bonded pairs, which are pulled away from the central
atom by outer atoms.

→ This leads to a relatively larger repulsive effect by the lone pairs & decreasing
angles in the order O > S > Se > Te and N > P > As > Sb.
Summary of Electronegativity and Atomic Size Effect
Outer atoms

X X Large electronegative X – repulsive effect of BP e ↓– angle↓

Size of the outer atom ↑ - angle ↑

Central atom

A Large electronegative A – increase conc of BP e’s near A

X - BP repel – angle ↑
X
X

All e’s –greater distances from each other, esp. for BP

pulled away from A – relatively larger repulsion of LP – angle ↓

X
3.2.3. Electronegativity and Atomic Size Effects
Electronegativity vs. Size
Electronegativity: CF3 > CH3
Size : CF3 < CH3

Size Determine the Molecule Geometry

Stronger Repulsive Effect on Axial Position

90o-90o Interaction: 3 (axial) vs. 2 (equatorial)

3.2.3. Electronegativity and Atomic Size Effects
Less Electronegative: Equatorial (Similar to Lone Pair)

The Effect of Electronegativity Difference is Small

 3.2.3. Electronegativity and Atomic Size Effects
Does Electronegativity Difference Explain Geometry Completely?

Just Symmetric Geometry is Favored!

Group Electronegativity
3.2.3. Electronegativity and Atomic Size Effects

 Electronegativity  X-S-X
OH-CH3 (0.9) vs. F-Cl (1.324) OH-CH3 (1.3) vs. F-Cl (4.2)

Bond Angle Determined by Multiple Factors (Size, hydrogen bonding)!

3.3. Molecular Polarity
• Combination of atoms w/ different electronegativities
- the resulting molecule has polar bonds;
• The greater the difference in electronegativity, the more polar the bond.
• This polarity causes specific interactions between molecules,
depending on the overall structure of the molecule.
• Experimentally, the polarity of molecules is measured indirectly by
measuring the dielectric constant

• Dipole moment (μ) for the molecule,

μ = Q·r
(Q: the charge on each of two atoms separated by a distance r)
3.3. Molecular Polarity
The dipole moments of NH3, H2O, NF3 - reveal the dramatic effect of lone pairs.

• In NH3, the averaged N-H bond polarities & the lone pair
- all point in the same direction → resulting in a large dipole moment

• H2O has an even larger dipole moment

← because the polarities of the O-H bonds & the two lone pairs
→ results in polarities all reinforcing each other.

• NF3 has a very small dipole moment,

← the result of the polarity of the three N-F bonds opposing polarity of the lone pair.
- sum of the 3 N-F bond moments - larger than the lone pair effect
- & the lone pair is the positive end of the molecule.
 3.3. Molecular Polarity
• Molecules w/ dipole moments interact electrostatically w/ each other & w/ other polar
molecules.
• Intra- or inter-molecular attractions → higher melting & boiling points.
ex. - hydrogen bonding (later in this chapter)

• Molecule - symmetric structure or if the polarities of different bonds cancel each other,
→ as a whole may be nonpolar, even if the individual bonds are quite polar.

ex). Td molecules (CH4 & CCl4)

Trigonal molecules & ions such as SO3, NO -, and CO 2-
3 3
- all nonpolar.
- The C-H bond has very little polarity,
but the bonds in the other molecules & ions are quite polar.
- In all these cases, the sum of all the polar bonds is 0
because of the symmetry of the molecules.
 3.3. Molecular Polarity

• Nonpolar molecules, still have intermolecular attractive forces acting on them.

• Small fluctuations in the e density in such molecules

→ create small temporary dipoles, w/ extremely short lifetimes.
→ These dipoles in turn attract or repel e’s in adjacent molecules
→ The result is an overall attraction among molecules.

• These attractive forces are called “London or dispersion forces”

→ make liquefaction of the noble gases & nonpolar molecules

such as hydrogen, nitrogen, & carbon dioxide

• In general, London forces are more important when there are more e’s in a molecule,
because the attraction of the nuclei is shielded by inner e’s & the e cloud is more
polarizable.
3.4. Hydrogen Bonding
NH3, H2O, HF- all have much higher b.p. than other similar molecules.

High b.p. ← Hydrogen bonds,

H atoms bonded to O or F also
form weaker bonds to a lone
pair of e’s on another O or F.

Polar δ-X−Hδ+ ··· :Z

The strongly positive H & the strongly negative lone pairs

→ line up & hold the molecules together.

Other atoms w/ high electronegativity (Cl)

- can also form H-bonds4i1n strongly polar molecules (chloroform, CHCl )
 3.4. Hydrogen Bonding
In general, b.p. rise w/ increasing M.W.

← the additional mass requires higher T for rapid movement of the molecules
& the larger # of e’s in the heavier molecules provides larger London forces.

- The difference in T between the actual b.p. of H2O & the extrapolation of the line
connecting the b.p. of the heavier analogous compounds is almost 200 °C.

- NH3 & HF have similar but smaller differences from the extrapolated values for their
families.
- H2O - much larger effect ← each molecule can have as many as 4 H-bonds
(two through the lone pairs & two through the H atoms).

- HF can average no more than two, because HF has only one H available.

F F
H H H H
F F
 3.4. Hydrogen Bonding
NH3
- can accept a H & form a H-bond through the lone pair on the N atom with H2O, HF, &
other polar molecules,
but it does not readily donate a H atom to another molecule.

On the other hand, H donation from N to carbonyl oxygen (CO) is common in proteins
& H-bonding in both directions to N is found in the DNA double helix.
 3.4. Hydrogen Bonding
Other unusual properties of H2O due to H-bonding.
Much higher freezing point of water than that of similar molecules.
The decrease in density as water freezes.

The Td structure around each O atom w/ two regular bonds to H & two H-bonds to other
molecules
- requires a very open structure w/ large spaces between ice molecules.
→This makes the solid less dense than the more random liquid water surrounding it, so ice
floats.
 3.4. Hydrogen Bonding
Coiling of protein & polynucleic acid molecules
In Figure 3-28(a), H-bonds between carbonyl oxygen & H’s attached to N hold the
molecule in a helical structure.

In Figure 3-28(b), similar H-bonds hold the parallel peptide chains together;
→ the pleated appearance of the sheet formed by the peptides.