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With this theory, the bonding between the central metal atom and the ligands is completely ignored.

The ligands are viewed simply as mere point charges. One focuses on the valence d orbitals of the central transition metal atom and examines how the relative energies of the d orbitals change upon introduction of external negative point charges (the ligands). Thus, it is necessary to go back and examine the various d orbitals. Octahedral geometry In the figure below, an octahedral field created by six point charges is assumed: If the distribution of the point charges is spherical then all d orbitals will be affected in the same manner. All of the d orbitals will rise in energy. In an octahedral arrangement, the point charges approach the metal atom along the Cartesian x, y and z axes. Thus, the orbitals that lie along these axes (dz2 and dx2-y2) should rise in energy by a greater amount compared to the orbitals that do not lie exactly along the x, y and z axes (dxy dxz dyz). The d orbitals in the presence of an octahedral field can be described by the following energy diagram:

With the above diagram in mind, one can therefore assign electronic configurations for various octahedral complexes:

Crystal Field Theory

It is straightforward as long as the number of d electrons is less than or equal to 3 (or greater than or equal to 8).

With 4 to 7 d electrons, two options are possible for octahedral complexes. An example is Co3+ in an octahedral complex:

Hexafluorocobaltate(III), [CoF6]3-, is characterized by a smaller crystal field splitting (the energy difference between the two sets of d orbitals). As a result, electrons choose to occupy the higher d orbitals instead of pairing with another electron (pairing has an energy penalty since electrons repel each other). On the other hand, hexaamminecobalt(III), [Co(NH3)6]3+, has a much larger crystal field splitting. In this case, the d electrons are forced to pair. The result is a configuration that is diamagnetic. High spin corresponds to a higher number of unpaired electrons while low spin corresponds to the opposite. Crystal Field Theory indeed becomes attractive when one has spectroscopy as a tool. The crystal field splitting is a measurable quantity. From various experiments, one can establish an empirical scale that ranks ligands according to increasing crystal field splittings: Cl- < F- < H2O < NH3 < ethylenediamine (en) < NO2- < CN-, CO Unfortunately, the above ranking raises serious questions against the crystal field theory since a neutral ligand, CO, is found to be one of the strongest ligands. Square planar geometry This should be similar to the octahedral case. In fact, one can imagine slowly removing the point charges along the z axis until they are completely gone. The figure below shows the correlation diagram:

Based on the energies of the d orbitals for a square planar complex, one would predict that this arrangement would be quite popular for d8 species. Tetrahedral geometry Imagine the metal atom inside a cube with its dz2 and dx2-y2 orbitals pointing at the center of the cube faces. In a tetrahedral arrangement, the point charges approach via the four opposite corners of the cube. The orbitals dxy, dxz, and dyz are pointing towards the center of the cube edges

Table 3.5Crystal

field

stabilization

energies

for

octahedral,

tetrahedral,

and

square

complexes (in units of o).

The Jahn-Teller Theorem does NOT say how large a distortion should occur. The distance between atoms is displayed in response to mouse clicks, click on the Cu(II) then click on a coordinating atom to see the distance. Determine the 6 bond lengths around each Cu(II) ion, I've started you off by showing 1 bond length for each. Having found the others, determine whether the molecules correspond to elongation or contraction of 2 bonds (the z-direction).

Weak Field (High Spin)

Strong Field (Low Spin)

System Examples Square


d0 d1 d2 d3 d4 d5 d6 d7 d8 d9 d10 Ca2+, Sc3+ Ti3+ U4+ Ti2+,V3+ V2+, Cr3+ Cr2+,Mn3+ Mn2+,Fe3+,Os3+ Fe2+,Co3+,Ir3+ Co2+,Ni3+,Rh2+ Ni2+,Pd2+,Pt2+,Au3+ Cu2+,Ag2+ Cu+,Zn2+,Cd2+, Ag+,Hg2+,Ga3+

Oct.

Tet.

Square

Oct.

Tet.

0 0.4 0.8 1.2 0.6 0 0.4 0.8 1.2 0.6 0

0 0.27 0.54 0.36 0.18 0 0.27 0.54 0.36 0.18 0

0 0.51 1.02 1.45 1.22 0 0.51 1.02 1.45 1.22 0

0 0.4 0.8 1.2 1.6 2.0 2.4 1.8 1.2 0.6 0

0 0.27 0.54 0.81 1.08 0.90 0.72 0.54 0.36 0.18 0

0 0.57 1.02 1.45 1.96 2.47 2.90 2.67 2.44 1.22 0

Apparent exceptions to the theorem are probably examples of what has been called the "dynamic Jahn-Teller effect". In these cases either the time frame of the measurement does not allow the distortion to be seen because of the molecule randomly undergoing movement or else the distortion is so small as to be negligible. 2 marks Pi acceptor ligands which can accept electrons from the metal d orbital into there anti bonding orbital such as CO, or C=C

The Jahn-Teller Theorem


The Jahn-Teller Theorem (named after Hermann Arthur Jahn and Edward Teller), was published in 1937 and essentially means that: "any non-linear molecular system in a degenerate electronic state will be unstable and will undergo distortion to form a system of lower symmetry and lower energy thereby removing the degeneracy" In an octahedral crystal field, the t2g orbitals occur at lower energy than the eg orbitals. This is a reflection of the orientation of the orbitals since the t2g are directed between bond axes while the eg point along bond axes. The shielding effect this has on the electrons is used to explain why the Jahn-Teller effect is generally only important for odd number occupancy of the eg level. The effect of Jahn-Teller distortions is best documented for Cu(II) complexes (with 3 electrons in the eg level) where the result is that most complexes are found to have elongation along the z-axis.