2P32 Winter Term 2012-13 Principles of Inorganic Chemistry

Dr. M. Pilkington

Lecture 1 Recapping Important Concepts

Inorganic Chemistry and the Periodic Table

Bonding Models
Shapes of Molecules - Lewis Structures
Valence bond theory: cases of NH3 H2O and BF3
Lewis Acids and Bases
and bonds in CH2=CH2
The Shapes of Molecules Relationship between Lewis
Structure, VSEPR theory and VBT.

Assignment 1 Drawing Lewis structures and predicting the

shapes/geometries of molecules due after class Friday 11th January

1. Inorganic Chemistry and the Periodic Table

Carbon is only one element and has limited bonding modes,

oxidation states and coordination numbers.
But it does CATENATE well and forms MULTIPLE BONDS with
itself and other p-block elements especially N and O.

For the rest of the elements:

Wide range of electronegativity, oxidation states, coordination
numbers, ability to form multiple bonds and catenate etc

How can we make sense of such wide ranging behaviors?

We have a system called the Periodic Table. The Periodic Law

1860-1870 (Mendeleev and Meyer): A periodic repetition of
physical and chemical properties occurs when the elements are
arranged in order of increasing atomic weight [number]

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With the development of atomic theory and spectroscopic techniques
the modern Periodic Table has evolved:

2P32 C
Course O
Outline:
tli :
Lectures 1-16
Coordination Chemistry
of transition Metal ions
Lectures 17 34
Descriptive Inorganic
Chemistry Main Group
Elements.
Elements

2. Bonding Models:

In covalent species, electrons are shared between atoms.

In an ionic species, one or more electrons are transferred between
atoms to form bonds.

Modern views of molecular structure are, based on applying wave

mechanics to molecules; such studies provide answers as to how and
why atoms combine. Two such methods are:
1. Valence Bond (VB) approach- overlap of valence orbitals on
atoms to form bonds.
2. Molecular Orbital theory (MO) of bond formation allocates
electrons to molecular orbitals formed by the overlap (interaction)
of
f atomic
t mi orbitals.
bit ls

Familiarity with both VB and MO concepts is necessary as it is

often the case that a given situation can be approached using one
or the other of these models.

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3. Shapes of Molecules

Understanding the shapes of molecules is an important step in

being able to discuss and predict chemical properties. Although
here we discuss the shapes of simple molecules, this topic has
also important applications in the understanding of the behavior
of much larger molecules, e.g the shape of macromolecules in
biology is often important with respect to their biochemical
function

Lewis structures you need to be able to draw these.

Lewis presented a simple but useful method of describing the
arrangement
g off valence electrons in molecules.
Lewis structures give the connectivity of an atom in a molecule,
the bond order and the number of lone pairs and these maybe
used to derive structures.
Revise your first year notes.

Test Question
Draw the Lewis Structure of the Nitrato ion NO3-.

How many bonds, how many bonds?

What is the nitrogen-oxygen bond order?

Are there possible resonance structures, can you draw them?

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 Bond Order

Single bond - first order

Double bond = second order
Triple bond third order

Bond order is a measure of the number of bonding electron pairs

between atoms. Single bonds have a bond order of 1, double bonds have
a bond order of 2 and triple bonds (the maximum number) have a bond
order of 3. A fractional bond order is possible in molecules and ions that
have resonance structures. In the example of ozone, the bond order
would be the average
g of a double bond and a single
g bond or 1.5 (3
(
divided by 2). As the bond order becomes larger, the bond length
becomes smaller.

Remember atoms in the 3rd period or below e.g. P, I do not always obey
the Octet rule!

4. Valence Bond Theory

The Shape of Ammonia (NH3) VSEPR is important here.
Lewis Structure
Lone Pair

H N H
But why isnt the NHN angle 900?

We have to consider repulsions between the lone pair and valence electrons
actual structure:

N
H-N-H angle is just slightly smaller than 109.50
H H
The Nitrogen atom is Pyramidal
H
Ammonia is a polar molecule with N carrying a partial negative
charge. Molecular shape is important with respect to determining if
a molecule is polar or not.

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 Look at Valence Bond Theory (VBT)
2s 2p
N [He] 2s2 2p3

Hybridization
mix the orbitals -" like mixing together a red and white plant"

H 1s1 H HH

2 3
N [He] 2s 2p Hybridization of N = sp3

We know that sp3 hybrids have a 109.50 angle

N
H
H
H

Molecular Structure of NH3 - cannot see the lone pair on N but

there is a flattened lone pair
N
H H
H

The actual shape of NH3 is trigonal pyramidal (approximately tetrahedral

minus one atom).

Compared to H20
The O in H2O has 2 bond pairs and 2 lone pairs. Two corners of the
tetrahedron are missing because they are occupied by lone pairs, not
atoms. The shape is called bent. The H-O-H angle is less than NH3, due
to the greater repulsions felt with two lone pairs

Other molecules with 2 bond plus 2 lone pairs include OF2, H2S and SF2.
Bond angles vary, but all are significantly less than 109.50.

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 The Shape of BF3
Treat this as an exception to the octet rule.
(An atom obeys the octet rule when it gains, looses or shares
electrons to give an outer shell containing eight electrons with
the configuration ns2np6). Many molecules such as neutral
compounds of Boron simply do not contain enough valence
electrons for each atom to be associated with eight electrons.

2s 2p
2
B 2s 2p sp2 this leaves an empty 2p orbital
F 2s2 2p5
F

F
F
Six electrons around the Boron

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 This leaves an unused "p orbital" perpendicular to the plane of BF3

F
F B
F

But if we want B to have an octet how can we achieve this?

A hybrid of 4 resonance structures is the best Lewis representation for the real
strucure of BF3.

F F F F

B B B B
F F F F F F
F F

However...
In this structure with a double bond the fluorine atom is
sharing extra electrons with the boron.
The fluorine would have a '+' partial charge, and the boron a
'-' partial charge, this is inconsistent with the
electronegativities of fluorine and boron.

Conclusion - the Octet Rule breaks down here.

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 Evidence for a resonance structure comes from the B-F
distances measured in the solid state. They are shorter by ~15
pms compared to the B-F distances in BF4-. Generally as we
move from a single bond towards a double bond our bond
lengths shorten by approximately 15 ppms.

F B F

C-C
C C Distances CH3CH2 CH CH
CH=CH
155 ppm 140 ppm

BF3 Resonance

F
Rehybridize the Fs to sp2
B F
F

empty filled
fill d
'p' on B 'p' on F
The MO diagram is complex but the result for BF3 is one -
bond spread over 3 B-F links.

B F

F
empty filled
'p' on B 'p' on F

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 To Summarize: BF3

The B atom has three bond pairs in its outer shell.

shell Minimizing the
repulsion causes this molecule to have a trigonal planar shape, with the
F atoms forming an equilateral triangle about the B atom. The F-B-F
bond angles are all 120, and all the atoms are in the same plane.

5. Lewis Acids and Bases

BF3 reacts strongly with compounds which have an unshared pair

of electrons which can be used to form a bond with the boron:
BF3 Lewis Acid electron pair acceptor.
NH3 Lewis Base electron pair donor.

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6. versus -bonding
Ethene, C2H4, sp2

H H Two lobes one with a

positive sign the other
with a negative sign go Nodal Plane
though a node. fn = 0 (wave function)
H H i e no electron density
i.e.

p orbital not used in hybridization

The three sp2 hybrid orbitals arrange themselves as far apart as

possible - which is at 120 to each other in a plane. The remaining p
orbital is at right angles to them.
C-H overlap to give sigma bonds.

The two carbon atoms and four

hydrogen atoms would look like
this before they joined
together:

The various atomic orbitals which are pointing towards each other
now merge to give molecular orbitals, each containing a bonding pair
of electrons.

orbital no nodal planes

orbital one nodal plane containing the nuclei.

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 Notice that the p orbitals are so close that they are overlapping
sideways.
This sideways overlap also creates a molecular orbital, but of a
different kind. In this one the electrons aren't held on the line
between the two nuclei, but above and below the plane of the
molecule A bond formed in this way is called a pi bond.
molecule. bond

-orbital above and

below nodal plane

The -bond is protected but the -bond is sticking up and is

not protected by the rest of the molecule, hence these
electrons are exposed to reacting species and it is why alkenes
and alkynes are reactive.

7. Relationship between Lewis Structure, VBT,VSEPR

Valence Shell Electron Pair Repulsion Theory (VSEPR) enables us to
predict the shape of the central atoms electron pairs and in turn the
hybridization of the central atom.

Lewis Structure

Electron Pair Geometry (VSEPR) - non bonding electrons and bonded atoms

hybridization molecular geometry - only looks at shape of

atoms; not lone pairs

(VBT)

bond overlap

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 Methane, Ammonia, Water

109.5 107.5 104.5

Electron pair geometry: Tetrahedral Tetrahedral Tetrahedral

Molecular geometry : Tetrahedral Triangular pyramidal Bent/Angular

Electron pair = nonbonding electrons + bonded atoms

Molecular only looks at shape of atoms; not lone pairs

Number of Bonded Atoms Shape (e-pair Geometry) Hybridization

and Lone Pairs on Central
Atom
2 Linear sp

3 Trigonal Planar/ triangular sp2

4 Tetrahedral sp3

5 Trigonal Bipyramidal sp3d

6 Octahedral sp3d2

Examples:
1. H2O H O H

- electron pair geometry = tetrahedral (2 lp

and 2 bp)
- molecular shape = bent
- O hybrization = sp3

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2. XeF4 (36 electrons) F

six pairs of electrons around Xe

F Xe F lone pair geometry - octahedral
Xe = sp3d2 hybridized
F = sp3 hybridized
F

the lone pairs are far appart therefore the compound as a SQUARE PLANAR
molecular geometry.

F F
Xe
F F

A typical midterm/exam question would be:

1. Draw the Lewis Structure of XeF4
2. Give (i) the molecular shape, (ii) the electron pair geometry at
the central atom and (iii) the hybridization of the central atom.

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