Chemistry of Complex Compounds Paper (Part 1)

Anastazija Ristovska
The 18 Electron Rule

Every cyclopentane in this complex contributes 5 electrons, and the cobalt, as seen from
its electron configuration, contributes 9 electrons, 2 from its s valence orbital, and 7 from its d
valence orbital. Thats a total of 19 electrons, and according to the 8-electron rule any complex
that has other than 18 electrons interacting in its formation does not obey the 18-electron rule
and therefore is not very stable.

Tungsten i.e. wolfram contributes 6 electrons, whereas each CO group contributes 2

electrons , for a total of 18 valence electrons participating in the formation of this complex,
making it a very stable one.

Cobalt binds with the cyclopentane ring of indenyl, as well as with two Co molecules.
The cyclopentane ring contributes 5 electrons, and each of the CO molecules contributes 2
electrons or a total of 4 electrons coming from the CO molecules, i.e. a total of 9 electrons
coming from the ligands altogether. All the ligands are molecules and not ions in this case, which
means they dont do anything to stabilize the +2 charge of the cobalt ion, and the overall
complex has charge +2. Cobalt contributes 9 electrons from its valence shell, however two of
them are lost to make the positive ion, and the complex is formed using only 18 electrons and
for this reason it is not too stable.

In this complex cobalt contributes 9 electrons from its valence shell, and ammonium
contributes a pair of electrons per molecule (total 12 electrons), for a total of 21 electrons,
however 3 electrons a lost to form a stable ion with charge +3, and thus 18 electrons participate
in forming a very stable complex ion.

Another complex forms between ammonium and

cobalt in which the oxidation number of cobalt is
(II), and ammonia being a neutral molecule, this
leaves the overall charge of the complex ion be +2.
The point group the ion belongs to is Oh.

This complex which forms between

Platinum (II) and two different types of
ligands, ammonium and chlorine, both
pairs positioned trans to one another, has
an overall 0 charge because the platinum
+2 charge is neutralized by the two Cl-1
ions. The point group it belongs to is D2h.

The isomerism of this complex is meridional,

abbreviated in nomenclature as mer- , with the
three ammonium ligands being in a vertical
plane thats perpendigular to the horizontal
plane in which the three Cl ion ligands are all
found. The point group of this complex is C2v;
full name: mer-triamminetrichlorocobalt(III).

This complex, on the other hand, is the facial

isomer of the one on the image left, and its
name is fac-triamminetrichlorocobalt(III). Its
point group is different too (C3v). The
difference is that, in this isomer, if we imagine
a sphere with radius exactly as the bond
lengths between the metal and the ligands,
there is a way to place a plane right through
the center of the sphere such that the
ammonium ions will be on the right face of the
sphere, whereas the chloride ion ligands will be
on the left face of the sphere.

The d-orbitals of transition metals all have the same energy and are degenerate. However,
in a complex, the degeneracy is removed, partially or completely, depending on the type of ligand
that bonds with the metal. The complex formed belongs to a certain point group, and the point
group name is used to describe the field that causes the splitting of orbital energy levels. Every
ligand will bond with a certain metal forming a complex that belongs to a certain point group,
and the type of orbital energy splitting one ligand causes in one metal is different, but is directly
linked to the point group the complex belongs to, in fact, each point group field splits the energy
of d orbitals in a specific way characteristic for that point group. The Oh field for example splits
the unperturbed 3d-orbitals into the eg and t2g energy levels, the eg level being at an energy
higher than the original energy of the unperturbed orbitals, and the t2g level being at an energy
lower than the original energy of the unperturbed orbitals. Since 3 of the d orbitals are at a lower
energy than their original energy, and only two are at a higher energy, even for transition metals
with 10 electrons in their valence d orbitals the overall energy gets reduced, making binding with
the ligand energetically favorable. Moreover, for transition metal elements with less than 10
electrons in their valence d orbitals, the d electrons will first fill out the t 2g three orbitals and only
after that will they begin filling the eg orbitals.
The crystal field interaction energy of the ligand will depend on whether the ligand is
weak or strong.

For weak ligands, the crystal field interaction

energy will be low and thus the eg and t2g
energy levels will be close to one another,
making it easier and more favorable for
electrons that could had stayed paired in the t2g
orbitals to split because of an extended effect
of the Pauli exclusion principle and occupy the
eg orbitals as well. Because theyre not paired,
these electrons add up their spins and make for
a high-spin (HS) complex.

When a ligand is strong, the crystal field energy

is high and the energy difference between the
eg and t2g orbitals is too high for electrons in
the t2g orbitals to overcome, making the
electrons there stuck in pairs. Thus the
complexes of strong ligands with high crystal
field interaction energy are low spin (LS).