I.

Introduction
Tris(oxalato)metallates(III) is an example of a complex compound hashas a trivalent
metal ion and an oxo anion more specifically the oxalate anion as the ligand. An oxo ligand is a
bidentate ligand which can bind to metal ions due to two single-bonded oxygen atoms that are
capable of donating a pair of electron to the central atom giving an octahedral complex. The
oxalate ion is a versatile ligand because it can act as a mono,bi, tri and tetradentate ligand
(Karlin, 2009).Some ways on how an oxo ligand may bind to a central metal are shown below.




Figure 1.1. Different ways an oxalate ion can attach to a metal atom.
There are two different proposed theories explained the nature of metal-ligand
interaction in complexes. First is the Valence Bond Theory (VBT) which predicts metal complex
bonding arises from the overlap of filled ligand orbitals and vacant metal orbitals. The resulting
bond is known as the coordinate covalent bond.The formation of complex in this theory is an
acid-base reaction in which the metal act as Lewis acid and the ligand act as the Lewis base.
The secondary valence of the metal depends on the available orbitals for the formation of the
bond. The structure of the complex can be explained by hybridization of metal orbitals.
Crystal field theory (CFT) on the other hand, was originally developed to describe the
electronic structure of metal ions in crystals, where they are surrounded by anions that create
an electrostatic field with symmetry dependent on the crystal structure (Miessler et. al, 2014).
The energies of the d orbitals of the metal ions are split by the electrostatic field, and
approximate values for these energies can be calculated (Miessler et. al, 2014). Crystal field
theory was developed in the 1930s. Shortly afterward, it was recognized that the same
arrangement of electron-pair donor species around a metal ion existed in coordination
complexes as well as in crystals, and a more complete molecular orbital theory was
developed(Miessler et. al, 2014). The energy difference between the two groups, t
2g
and e
g
, is
denoted as
O
.
On the kind of ligand the complex have and the kind of metal ion it has was the
distribution of the d-electrons in these orbitals dependent. Weak field ligands are those with
small interactions with the metal, the split between the two groups is small, and therefore the
O
is small. For complexes with these ligands, all the d-orbitals are filled first before pairing
happens since
O
is smaller than the repulsive force between the paired electrons (Miessler and
Tarr, 2008). On the other hand, strong field ligands are those which have strong interactions
with the metal and therefore the split between the groups is large and
O
is also large. Therefore
for complexes with these ligands, pairing happens first since the
O
is larger than the repulsive
force (Miessler and Tarr, 2008).
Mn
2+
<V
2+
<Co
2+
<Fe
2+
<Ni
2+
<Fe
3+
<Co
3+
<Mn
4+
<Mo
3+
<Rh
3+
<Ru
3+
<Pd
4+
<Ir
3+
<Pt
4+

Figure 1.3. Relative field strengths of metal ions

C
O
C
O
O O
M C
O
C
O
O O
M
M
C
O
C
O
O
O
M
C
O
C
O
O
O
M
O
O
O
O
C
C
O
O
C
C
O
O

Figure 1.4.Spectrochemical series of ligands.


Figure 1.5.Distribution of d-electrons for complexes with weak field and strong field ligands.
The tris(oxalato)complexes synthesized in this experiment were the following:
K
3
[Al(C
2
O
4
)
3
]3H
2
O, K
3
[Cr(C
2
O
4
)
3
]3H
2
O, K
3
[Fe(C
2
O
4
)
3
]3H
2
O and K
3
[Co(C
2
O
4
)
3
]3.5H
2
O.




Figure 1.6. The general structure of the oxalate complexes synthesized.
Tris(oxalato) complexes of these metals are synthesized as racemic mixtures of two
enantiomers. They have identical physical and chemical properties yet they are distinguishable
by striking a plane of polarized light.

To measure the magnetic susceptibility, there are two methods that can be used: the
traditional Gouy method and the Evans method. In Gouy method, it makes use of the interaction
between unpaired electrons and a magnetic field. A glass of tube where the compound of
interest is placed was used in this method; this is then suspended from a balance and then
weighed. After that the tube is immersed in a strong magnetic field. The change in weight
caused by the attraction (for paramagnetic compounds) or the repulsion (diamagnetic) is
recorded and by measuring the force that this change of weight caused, the magnetic
susceptibility of the compound can be obtained (Miessler and Tarr, 2008). The Evans method
on the other handhas same principles as the Guoy method. However, it does not measure the
force the magnet exerts on the sample but the force that the sample exerts on a suspended
permanent magnet. It is also attached to an arm of a very sensitive balance where upon
introduction of sample in the balance magnetic deflection occurs. The deflected magnetic flux
can be brought back to equilibrium by passing a current into the coil proportional to the force
exerted by the sample(Woolins,2010).IR spectroscopy was supposedly done to characterize the
synthesized complexes.
C
O
C
O
O
O
M
O
O
O
O
C
C
O
O
C
C
O
O
The objectives of the experiment are to synthesize salts of tris(oxalato) complexes of Al
(III), Cr(III), Fe(III) and Co(III): K
3
[Al(C
2
O
4
)
3
]
.
3H
2
O, K
3
[Cr(C
2
O
4
)
3
]
.
3H
2
O, K
3
[Fe(C
2
O
4
)
3
]
.
3H
2
O and
K
3
[Co(C
2
O
4
)
3
]
.
3.5H
2
O.These compounds will also be characterized through magnetochemical
studies and IR spectroscopy.
References:
KARLIN,K.D. 2009.Progress in InorganicChemistry.Vol 56.John Wiley &Sons: New
Jersey.
MIESSLER, G.L., FISCHER P.J. and D.A. TARR.2014. .Inorganic Chemistry.5
th
Ed.
Pearson Education South Asia Pte.Ltd.: USA.
MIESSLER, G.L. and D.A. TARR, D.A. .2008.Inorganic Chemistry.3
rd
Ed. Pearson
Education South Asia Pte.Ltd.: Singapore.

WOOLINS,J.D. 2010. Inorganic Experiments..John Wiley &Sons.