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Bonding

There are many different approaches to describing


bonding
for elements with a large electronegativity difference it
is often easiest to view the bonding as arising from
electrostatic interaction between ions formed by the
complete transfer of electrons between atoms
when the electronegativity difference is not so large
bonding may be viewed as covalent and involving the
sharing of electrons by bonded atoms
equal sharing if there is no electronegativity difference,
unequal sharing if the electronegativities are different

Covalent bonding
Modern methods for describing bonding make use
of quantum mechanical methods and describe the
electrons in molecules in terms of molecular
orbitals
However, simpler earlier theories such as that due
to Lewis can be useful in some cases and they are
a lot less complex

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Lewis theory
Lewis theory of bonding was one one the
earliest to have any success
Based on the octet rule
main group elements like to have eight
electrons when they form compounds (except
hydrogen)
Works quite well for second period
elements but runs into problems with other
elements

Bond order
In many cases Lewis structures can be used
to calculate bond orders that correlate well
with experimentally measured bond
strengths and lengths
:N:::N: triple bond, bond order 3
O O double bond, bond order 2

2
Formal charges
A molecule may have more than one plausible
Lewis structure
The best Lewis structure is the one that has the
least charge separation and puts the negative
charge on the most electronegative elements

N N O N N O N N O
-1 +1 0 0 +1 -1 -2 +1 +1

Arrive at formal charges by dividing shared electrons


equally amongst the atoms they are shared over

Resonance structures
Molecules and ions with more than one distinct
but equivalent (by rotation or reflection etc.)
Lewis structures can occur. The real structure is
an average of these different resonance forms

Reality is the average of


Three distinct Lewis structures the three resonance forms
Bond order is 1.3333

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Failures of the Lewis model
A number of molecules with odd numbers
of electrons exist (no octet) e.g. NO
An atom may not have enough electrons to
complete its octet without having ridiculous
formal charges e.g. BF3
A central atom may clearly have more than
8 electrons e.g. SF6
O2 is paramagnetic!!

VSEPR
Valence Shell Electron Pair Repulsion theory
is a useful tool for predicting the geometrical
structures of main group compounds
Based on the idea that pairs (or groups) of
valence electrons (either bonding or lone
pairs) will try and avoid each other as much as
possible
molecule adopts a geometry that allows electron to
be as far apart as possible

4
Groups of electrons and geometry

Electron pair count and geometry


Two pairs on central atom - linear
Three pairs on central atom - trigonal
Four pairs on central atom - tetrahedral
Five pairs on central atom - trigonal
bipyramidal
Six pairs on central atom - octahedral
Seven pairs - a number of possibilities

5
Electron counting
For molecules with single bonds to the
central atom count all valence electrons of
central atom plus one electron for each
ligand atom
BCl3 3 electrons from boron and 1 from each
chlorine so there are 3 pairs of electrons
When there are double bonds present count
the four electrons associated with the
double bond as a single group

Linear geometry
Molecules with two groups of electrons
around the central atom

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Trigonal geometry

Repulsions amongst electron pairs/groups are not all the same.


Lone pairs require more space than bonding pairs. One non-bonding
electron requires less space than a bonding pair.

Tetrahedral geometry
Based on a tetrahedral arrangement of
electrons but...
molecular shape is the arrangement of atoms not electrons

Tetrahedral Pyrimidal V-shaped

7
TBP geometry
Lone pairs go equatorial to minimize repulsion
between lone pairs and other groups of electrons
axial
equatorial

Trigonal
bipyramidal
(b) preferred over (a)

linear Saw
T-shaped horse

Octahedral geometry
Lone pair avoid each as much as possible

Trans not cis lone pairs as


this minimizes repulsion
between lone pairs

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Species that violate VSEPR
Like nearly all truly useful sets of rules
there are exceptions
Transition metal compounds usually do not
follow VSEPR theory
Species that are sterically crowded often do
not obey VSEPR
XeF6 obeys VSEPR (7 pairs)
TeCl62- does not (7 pairs but is octahedral)