Oxygen has electronic configuration [He]2s22p4,
and has common oxidation states -2,-1, and 0. Other members of
the group show a tendency for hypervalence,
and have oxidation states from +1 to +6, eg. sulphur in SF6.
(For a comparison of the chemistries of oxygen and sulphur, click
here.)
There are two common allotropes of Oxygen: O2 and
O3 (Ozone).
O2
In its electronic ground state, this is
paramagnetic (has unpaired electrons),
has electron spin S=1 (it has a triplet ground state), and forms
a pale blue liquid and solid at low temperatures
Ground State of
O2: the 2πg
antibonding orbitals are each singly occupied, giving
an electron spin of 1. This is therefore a triplet state,
with term symbol 3Σg-. |
 |
| The excited state
of O2 has the electrons in the 2πg
antibonding orbitals paired, leading to the singlet state,
1Δg. |
The paired electrons
can take part in concerted Diels-Alder
type reactions:  |
O2 can be reduced to give O2+,
and oxidized to give O2- and O22-.
In the case of O2+, the
electron is removed from an antibonding orbital, and in the
other cases the extra electrons are added to antibonding orbitals.
The effect this has on the bond order, and therefore bond strength,
is shown in the table.
| Species |
No. of bonding electrons
(NB) |
No. of antibonding electrons
(NA) |
Bond Order: (NB-NA/2) |
| O2+ |
6 |
1 |
2.5 |
| O2 |
6 |
2 |
2 |
| O2- |
6 |
3 |
1.5 |
| O22- |
6 |
4 |
1 |
O2 is a π-acid
like N2 and CO, and so can act as a ligand in the
same way. This is very important as the transmission
of oxygen in blood is by the reversible binding of molecular
O2 (as O2-) to Fe atoms in
haemoglobin. O2 also
binds to other transition metals, eg. in the formation
of Vaska's complex:
| Formation of Vaska's complex |
 |
O3: Ozone
This is prepared by electrical discharge through O2, and has the bent
structure predicted by VSEPR theory with two resonance forms.
It is highly reactive, with a high positive Gibbs free energy
of formation.
| Resonance structure of Ozone: |
 |
Stereochemistry of Oxygen
Unicoordinate O:
E=O bonds are very common
Bicoordinate O:
E-O-E groups are typically bent (as predicted by VSEPR), but
the formation of Edπ-Opπ
interactions tend to favour linear arrangements.
Tricoordinate O:
this is typically pyramidal, eg. in +OR3,
but is trigonal planar in some OM3 complexes.
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