Did We Forget Square Planar Complexes?

 Imagine that we have an octahedral complex from which we are removing the
axial ligands. As ligands move away along the z-axis, d-orbitals with a z-
component will fall in energy.
 The dz2 orbital falls the most, as its electrons are concentrated in lobes along
the z-axis.
 The dxz and dyz orbitals also drop in energy, but not as much.
 Conversely, the d x2-y2 and the dxy orbitals increase in energy. The splitting
diagram for square planar complexes is more complex than for octahedral
and tetrahedral complexes, and is shown below with the relative energies of
each orbital.
 Tetragonal Distortion
 Intermediate stages will lead to a “distorted” octahedral complex.
Square Planar Crystal Field
 Square Planar Complexes
 Why would a "happy" octahedral complex want to lose two of its ligands to
make a square planar complex?

 Square planar coordination is rare except for d8 metal ions. Occasionally,

d9 complexes with large ΔO also occur.  3d8 complexes with strong field ligands
and 4d8, 5d8 complexes with any ligands can be expected to be square planar.

 Examples of such d8 complexes are [Ni(CN)4]2-, the anti-cancer drug cisplatin

(cis-Pt(NH3)2Cl2), [Pd(H2O)4]2+, and [AuCl4]-.

 At the d8 electron count, the lowest four orbitals are filled and the highest
orbital (the dx2-y2) is empty, resulting in a large CFSE. These complexes are
diamagnetic and tend to be quite stable.
The crystal field stabilization energy for a diamagnetic square planar d 8 metal
complex is readily calculated by the usual method:

8 8
The pairing energy correction is included because a free d ion has 2 unpaired electrons, but a square planar d

complex has no unpaired electrons

 Square Planar Complexes: General Trends
 As a result of these distortions, there is a net lowering of energy (an increase
in the ligand field stabilization energy) for complexes in which the metal has a
d7, d8, or d9 configurations, and thus electrons would occupy the upper eg set
if an octahedral complex.
 In general, the size of the splitting in a square planar complex, DSP is 1.3 times
greater than Do for complexes with the same metal and ligands.  As a result,
the distortion results in square planar complexes with lower energies  than
the comparable octahedral complex. 
 This distortion to square planar complexes is especially prevalent for
d8 configurations and elements in the 4th and 5th periods such as:  Rh (I), Ir (I),
Pt(II), Pd(III), and Au (III).  Nickel (II) four-coordinate complexes are usually
tetrahedral unless there is a very strong ligand fields such as in [Ni(CN)4]2-,
which is square planar.
Nickel(II) vs. platinum(II): why is Pt2+ found only in
square planar coordination but Ni2+ is found in
several geometries?
 Nickel forms the octahedral hexaammine complex, [Ni(NH3)6]2+, but platinum
forms the square planar tetraammine complex [Pt(NH3)4]2+. Both metal ions
have 8 d-electrons.
 We can calculate a preference energy for octahedral over square planar
coordination, just as we did for octahedral over tetrahedral. We will neglect
the pairing energy for this calculation. 
 Nickel(II) vs. platinum(II)
 Notice that in this case, the crystal field stabilization (in terms of Do) is
much greater for square planar coordination than for octahedral
coordination! In fact, the preference energy (compared to octahedral
coordination) for square planar coordination of a d8 metal ion is -1.24 Do.

 However, let's use the following values and determine the absolute values
for the square planar preference in kJ/mol.
Do
Complex
(kJ/mol) 
[Ni(NH3)x]2+ 132
[Pt(NH3)x]2+ 359
2+
Preference for square planar coordination by [Ni(NH3)x] = -1.24 (132 kJ/mol) = -164 kJ/mol

2+
Preference for square planar coordination by [Pt(NH3)x] = -1.24 (359 kJ/mol) = -445 kJ/mol
 Nickel(II) vs. platinum(II)

 Thus square planar [Pt(NH3)4]2+ is stabilized by nearly 300 kJ/mol more

than the corresponding nickel complex. This greater energy difference is
enough to make up for the loss in bond energy suffered as an octahedral
platinum(II) complex is transformed to a square planar complex, but is
not usually enough to favor square planar complexes for nickel.

 So why does nickel form square planar complexes at all?

Actually, there are many fewer square planar complexes than there are
octahedral ones. the ones that are square planar tend to be found with
stronger-field ligands, i.e. those that are capable of giving high values for
the octahedral splitting energy Do.
Magnetism in Macroscopic Setting

S
 Magnetism in Macroscopic Setting

A pioneering experiment
by M. Faraday
« Farady lines of forces »
about magnetic flux N

S
Magnetism in Macroscopic Setting

N
N

S
S
attraction
N
N

S
S
Magnetism in Macroscopic Setting

S N

repulsion
N N

S
S
Bulk Property as Cumulative Effect of Atomic
Magnetic Moments

N
many many
   sets of  sets of
domains
S atomic
magnetic
moments
 Magnetic Properties of Coordination Complexes
 Some substances are attracted to magnetic field.

 Some substances are repelled too.

Magnetic field “on”
Substance is paramagnetic

Magnetic field “off”

Magnetic field “on”

Substance is diamagnetic
 What Causes Paramagnetism?
Diamagnetic Compounds: Those, which tend to move out of a magnetic field.
Example: N2

Paramagnetic Compounds: Those, which tend to move into a magnetic field.

Example: O2

 The extent of paramagnetism is measured in terms of the magnetic moment, μ. The

larger the magnitude of μ, greater the paramagnetism of the compound.

 Magnetic moment has contributions from spin (S) and orbital angular momentum (L). A
non-spherical environment may lead to quenching of the contribution from orbital
angular momentum.
What Causes Paramagnetism?
 Magnetic Properties of Coordination Complexes
 Effective magnetic moment (μ )= [L(L+1) + 4S(S+1)] 1/2
eff

For a given value of the orbital quantum number l, the magnetic quantum
number m can have any values from –l to +l including 0 (zero) and L = Sm

For d-orbital electrons, l = 2, so, m= 2, 1, 0, -1, -2

If there is only one electron in the d-orbitals, L= 2

 Experimental μ values effectively used to differentiate high-spin or low-

spin states of complexes.
 For 1st row transition metal ions, effect of L on μ is small and μeff correlate
fairly well with those derived from the spin-only formula.

eff = s.o. = 2{S(S+1)}1/2 B (B is the Bohr magneton)

In terms of number of unpaired electrons “n”

 =  = {n(n+2)}1/2 
Magnetic Properties of Coordination Complexes
 Using the Spectrochemical Series to predict magnetic properties.

 How many unpaired electrons would you expect to find in the

octahedral complex [Fe(CN)6]3-?

Fe [Ar]3d64s2

Fe3+ [Ar]3d5
 Magnetic Properties of Coordination Complexes
Using the Crystal Field theory to Predict the Structure of a Complex from Its
Magnetic Properties.
 The complex ion [Ni(CN4)]2- is diamagnetic. Use ideas from the crystal field
theory to speculate on its probable structure.
 Coordination is 4 so octahedral complex is not possible.
 Complex must be tetrahedral or square planar.
 Draw the energy level diagrams and fill the orbitals with e-.
Consider the magnetic properties.
Solution:
Tetrahedral: Square planar:
 Some Calculations and Observations
 The spin-only formula applies reasonably well to metal ions from the
first row of transition metals: (units = μB,, Bohr-magnetons)

 = {n(n+2)}1/2 B where n = no. of unpaired electrons

Metal ion dn configuration μeff(spin only) μeff (observed)

Ca2+, Sc3+ d0 0 0
Ti3+ d1 1.73 1.7-1.8
V3+ d2 2.83 2.8-3.1
V2+, Cr3+ d3 3.87 3.7-3.9
Cr2+, Mn3+ d4 4.90 4.8-4.9
Mn2+, Fe3+ d5 5.92 5.7-6.0
Fe2+, Co3+ d6 4.90 5.0-5.6
Co2+ d7 3.87 4.3-5.2
Ni2+ d8 2.83 2.9-3.9
Cu2+ d9 1.73 1.9-2.1
Zn2+, Ga3+ d10 0 0
When does Orbital Angular Momentum Contribute?
Essential conditions:
1. The orbitals should be degenerate (t2g /t2 or eg/e)

2. The orbitals should have similar shape and size, transformable to each other
by rotation.

3. Orbitals must not be symmetrically occupied (half-filled/full-filled).

For an octahedral complex, orbital contributions are possible only when the t2g
orbitals are differentially occupied and for a tetrahedral complex the t2 orbitals
have to be differentially occupied.
When does Orbital Angular Momentum Contribute?
 Ferromagnetism
 In a normal paramagnetic material, the atoms containing the unpaired electrons are
magnetically dilute, and so the unpaired electrons in one atom are not aligned with
those in other atoms.

 However, in ferromagnetic materials, such as metallic iron, or iron oxides such as

magnetite (Fe3O4), where the paramagnetic iron atoms are very close together, they can
create an internal magnetic field strong enough that all the centers remain aligned:
 Antiferromagnetism
 Here the spins on the unpaired electrons become aligned in opposite
directions so that the μeff approaches zero, in contrast to ferromagnetism,
where μeff becomes very large.

 An example of anti-ferromagnetism is found in MnO.

 Back to Structures and Geometry…….
 So far we have considered “perfect” geometries, i.e., we expect a complex of
the type ML6 to have all bonds equivalent. But….
 Distorted Octahedral Complex
 Not all complexes exhibit such distortion.
 This phenomena is referred to as Jahn-Teller distortion
 The Jahn-Teller Theorem
 The Jahn-Teller (J-T) theorem states that in molecules/ ions that have a
degenerate ground-state, the molecule/ion will distort to remove the
degeneracy.
This is a fancy way of saying that when orbitals in the same level are
occupied by different numbers of electrons, this will lead to distortion of the
molecule.
For us, what is important is that if the two orbitals of the eg level have
different numbers of electrons, this will lead to J-T distortion.

High-spin Ni(II) – only one way of filling

the eg level – not degenerate,
no J-T distortion
 Further Splitting of the t2g and eg Levels
 The CF view of the splitting of the d-orbitals is that those aligned with the two
more distant donor atoms along the z-coordinate experience less repulsion
and so drop in energy (dxz, dyz, and dz2), while those closer to the in-plane
donor atoms (dxy, dx2-y2) rise in energy.
 Lowering of energy (although small) is the motivation behind distortion.
 J-T Distortion for d1 System
 in molecules/ ions that have a degenerate ground-state, the molecule/ion
will distort to remove the degeneracy.
 Comparison of d1 and d9 Systems

Z-out Z-in

 Distortions are more pronounced if degeneracy occurs in an eg orbital.

 General Picture

Z-out Z-in

 Distortions are more pronounced if degeneracy occurs in an eg orbital.

J-T Distortion Possibilities for High-Spin
Octahedral Complexes
J-T Distortion Possibilities for Low-Spin
Octahedral Complexes
Will a d2 system Exhibit Compression or Elongation?