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1. Bonding
1.1 Crystal Field Theory
2. Spectroscopic Properties
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Introduction
Crystal field theory takes the ionic approach and considers the ligands as point
charges around a central metal positive ion, ignoring any covalent interactions.
The negative charge on the ligands is repelled by electrons in the d-orbitals of
the metal. The orientation of the d-orbitals with respect to the ligands around
the central metal ion is important, and can be used to explain why the five d-
orbitals are not degenerate (= at the same energy). Whether the d-orbitals point
along or in between the cartesian axes determines how the orbitals are split into
groups of different energies. We shall examine the splitting of d-orbitals for
octahedral, square planar and tetrahedral ligand geometries.
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The Octahedral Crystal Field
Question 1.1.1
Which of the d-orbitals point directly towards the ligands?
d xy d xz d yz d z2 d x2-y2
There is repulsion between the electrons in the d-orbitals and the lone pairs on
the ligands. This has a destabilizing effect on the d-orbitals. In a spherical field
all five d-orbitals would be raised in energy by the same amount. However,
electrons in the orbitals pointing towards the ligands are repelled by the ligand
lone pair to a greater extent than those pointing in between the ligands, because
they are closer. Hence, the dz2 and dx2-y2 orbitals are destabilized to a greater
extent than the dxy, dxz and dyz orbitals, and the degeneracy is removed.
We can now construct the d-orbital splitting diagram for an octahedral field.
The d-orbitals for an octahedral complex are split as shown in the diagram
below.
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The two sets of orbitals are labelled eg and t2g and the separation between these
two sets is called the ligand field splitting parameter, o. The subscript o is used
to signify an octahedral crystal field. o will be discussed in more detail later.
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metal ion, and there is electrostatic repulsion between the ligands and electrons
in the d-orbitals.
None of the d-orbitals point directly at the ligands as they did with the
octahedral geometry. However some orbitals come closer to the ligands than
others.
Question 1.1.2
Draw the tetrahedral configuration looking down the z-axis and draw the d-
orbitals to find those with the biggest interaction:
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The two sets of orbitals are labeled e and t2. The subscript g is not needed here,
it is only used for systems that possess a centre of symmetry (tetrahedral systems
do not have a centre of symmetry). The separation between the two sets of
orbitals is t (the subscript t signifies a tetrahedral crystal field). It should be
noted that t is smaller than o;
t 49o
Removing these two ligands has the effect of stabilizing the orbitals which point
directly or partially along the z-axis. That is, the dz2, dyz and dxz orbitals are
stabilized. Electrons in these orbitals suffer less repulsion than in an octahedral
field, and so are lowered in energy. As the dz2 orbital points directly along the z-
axis it is stabilized to a greater extent than the dyz and dxz orbitals, which point
in between the z-axis.
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Crystal Field Splitting Parameters
In an octahedral or a tetrahedral crystal field, the d-orbitals are split into two
sets. The energy separation between them is called the crystal field splitting
parameter. It is given the symbol o (for an octahedral crystal field) or t (for a
tetrahedral crystal field).
In both cases the overall stabilization of one set of orbitals equals the overall
destabilization of the other set. In the octahedral crystal field the overall
stabilization of the t2g set equals the overall destabilization of the eg set. If the eg
set is raised by two units, the t2g set is lowered by three units to achieve this
energy balance. Therefore, the eg set is raised by 0.6o and the t2g set is lowered
by 0.4o. Note that some texts will use 10Dq instead of o, these are equivalent.
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Bary Center
If all other things are equal, then t is smaller than o. t 49o 12o
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Crystal Field Stabilization Energy (CFSE)
Octahedral Complexes
x y
For the general configuration t2g eg the CFSE is
For a d4 system it is clear that there are two possibilities. The fourth electron can
4 0
go into the t2g set or into the eg set, corresponding to configurations t2g eg (low
3 1
spin arrangement) and t2g eg (high spin arrangement), respectively.
If the fourth electron goes into the t2g set there would be an energy penalty
associated with the pairing of electrons. This is called the pairing energy, P. The
CFSEs are then -1.6o + P (for the low spin case) and -0.6o (for the high spin
case). Both low and high spin arrangements arise in practice, and which
configuration is adopted depends on the size of o.
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For large values of o: o > P
complex will be low spin
Question 1.1.3
Which of the following compounds has a CFSE of 0.0o associated with it?
[PtF6]
[Fe(CN)6]3-
[Mn(OH2)6]2+
The Fe2+ ion is d6 and has a pairing energy of approximately 17000 cm-1 (this is 2.1
eV or 200 kJ mol-1). (The pairing energy varies somewhat with the coordination
environment.) For [Fe(H2O)6]2+, o = 10000 cm-1.
Because P > o, [Fe(H2O)6]2+ is a high-spin complex. The electron configuration is
(*)4 (*)2 and the total spin is 2. (Note that water is a weak -donor ligand.) On
the other hand, for [Fe(CN)6]4- o = 33800 cm-1, and this complex is low-spin (P <
o). All six d electrons reside in the low lying () orbitals (cyanide is an excellent
-acceptor ligand), leading to a total spin of zero.
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Tetrahedral Complexes
The procedure for working out the CFSEs for tetrahedral complexes is the same
as that for octahedral complexes. However, as the energies of the two set of
orbitals are reversed (the e set is lower in energy than the t2 set) the CFSE for a
t2xey configuration is now:
As t is less than half the size of o, then normally all tetrahedral complexes are
high spin. This is because the pairing energy P is almost always larger than the
splitting between the two energy levels.
Question 1.1.4: Calculate the CFSE of the following molecules - do you expect
high- or low spin configuration ?
[CoCl4]2-
[ReO4]-
[FeCl4]-
The size of the energy gap between the t2g and eg levels, o, depends on 3
factors:
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Oxidation State of the Transition Metal
As the oxidation state of the transition metal (effectively the charge on the
metal) is increased, the surrounding ligands are attracted more closely to the
metal centre. The orbitals on the ligands interact more strongly with the d-
orbitals and o increases.
Question 1.2.1
Which of the following two complexes would have the smallest value of o?
A. [Fe(OH2)6]3+
B. [Fe(OH2)6]2+
On going from the first to the second row of a transition metal triad, there is
approximately a 50% increase in the size of o, and another 50% increase on going
from the second row to the third row. This is due to the fact that as you descend
a transition metal triad the size of the d-orbitals increases (3d < 4d < 5d). The
larger d-orbitals interact more with the orbitals on the ligands, hence o is
larger. It should also be noted that the pairing energies for the larger d-orbitals
are smaller, which means that low spin configurations are favoured.
Question 1.2.2
Which of the following would have the smallest value of o?
A. [Os(OH2)6]3+
B. [Fe(OH2)6]3+
C. [Ru(OH2)6]3+
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Ligand
CN- = CO = C2H4 > PR3 > NO2- = phen > bipy > SO32- > en = py = NH3 > edta4- > NCS-
> H2O > C2O42- > ONO2- > OSO32- > OH- = ONO- > F- > Cl- = SCN- > Br- > I-
Weak field ligands, such as Cl- and SCN-, give rise to small values for o, while
strong field ligands, such as CN- and CO, give rise to large values for o.
Mn2+ < Ni2+ < Fe2+ < V2+ < Fe3+ < Co3+ < Mn3+ < Mo3+ < Rh3+ < Ru3+ < Pd4+ < Ir3+ < Pt4+
Question 1.2.3
Which of the following would have the largest value of o?
A. [Cr(OH2)6]3+
B. [CrF6]3-
C. [Cr(NH3)6]3+
D. [Cr(NH3)6]2+
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Sigma Bonding Interactions
From:
http://chemwiki.ucdavis.edu/Inorganic_Chemistry/Crystal_Field_Theory/Virtual%3a_Electronic
_Structure/Ligand_Properties
The Lewis acid-base reaction between the metal and the ligand results in a set of
low energy, fully
occupied (because
the original ligand
donor orbitals were
fully occupied)
bonding orbitals that
are primarily
localized on the
ligand and a set of
high energy *
orbitals that are
primarily localized on
the metal. Three of the metal orbitals (dxy, dxz, and dyz) do not interact with the
ligand orbitals and remain as nonbonding orbitals completely centered on the
metal.
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The d-orbital splitting, o, arises from the increase in energy of the * orbitals
relative to the nonbonding orbitals. The stronger the bonding interaction, the
higher the * energy and the greater o. A strong bonding interaction requires a
good energy match between the metal and the ligand. Empirically, there is a
correlation between o and the basicity of the ligand. A ligand that is a good
Brnsted (or Lewis) base tends to form strong bonds with metals and thus
produces a relatively large o.
Pi Bonding Interactions
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1.3 The Jahn-Teller Effect
Jahn-Teller theorem
Example of complexes
Nature of the distortion
Explanation of why it occurs
Jahn-Teller Theorem
In 1937 H.A. Jahn and E. Teller put forward a theorem which explained some of
the distortions observed in transition metal complexes. This became known as
the Jahn-Teller theorem. It states:
These distortions are called Jahn-Teller distortions. But how are the molecules
distorted, and how does the distortion occur? This section aims to describe what
is meant by an electronically degenerate state and explain how Jahn-Teller
distortions can lower the energy of molecules in such states.
There are some complexes which might at first be expected to be octahedral, but
which are in fact distorted from the ideal octahedron. These distortions are
called Jahn-Teller distortions. One notable example is the complex ion
[Cu(OH2)6]2+, shown below. Two of the metal-ligand bonds are longer than the
other four. This type of distortion is called a tetragonal elongation.
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Another example is KCrF3. In this compound Cr is in oxidation state II and is high
spin d4. There are four long Cr-F bonds and two short Cr-F bonds. This type of
distortion is called a tetragonal compression.
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For comparison, below is the [Ni(OH2)6]2+ complex ion, which is symmetrical and
undistorted:
Explanation
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If the electron goes into the dz2 orbital there will be a greater amount of charge
density along the z axis. This means that the ligands along the z axis cannot
approach as closely as when the dz2 orbital is singly occupied, as there will be
more repulsion between the electrons in the dz2 orbital and the ligand lone pair.
The ligands which lie on the z-axis move out a bit and the other ligands move in a
bit, as they now suffer less repulsion - the complex ion will be tetragonally
elongated. The ligands along the z axis are further away from the metal, which
means the energy of the dz2 orbital is lowered with respect to the dx2-y2 orbital.
The energy of t2g set is also affected, but to a lesser extent. The dxz and dyz
orbitals (which have components along the z axis) interact less with the z axis
charges and are lowered in energy relative to the dxy orbital. The degeneracy of
the orbitals is lifted and the overall energy of the complex is lowered, as stated
by the Jahn-Teller theorem.
Question 1.3.1
Which of the d-orbitals are raised in energy as a result of a tetragonal elongation?
d xy d xz d yz d z2 d x2-y2
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If the electron goes into the dx2-y2 orbital there will be a greater amount of charge
density along the x and y axes. Ligands along the x and y axes cannot approach as
closely as when the dx2-y2 orbital is singly occupied, which results in the ligands
centered on the x and y axes being further away from the metal. The bond
lengths along the z axis will be shorter than those on the x and y axes. This
distortion is called a tetragonal compression. The energies of the orbitals with
components in the x-y plane are stabilized relative to the other orbitals. The dx2-y2
orbital is stabilized to a greater extent than the dxy orbital since it points more
directly towards the ligands. Again the degeneracy is lifted and the overall
energy is lowered.
Question 1.3.2
Which of the d-orbitals are raised in energy as a result of a tetragonal
compression?
d xy d xz d yz d z2 d x2-y2
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Elongation results in a greater stabilization than compression; this explains why
the [Cu(OH2)6]2+ ion is tetragonally elongated.
Example: [Ti(OH2)6]3+ : Ti is in oxidation state III. Ti is d1, and the electron can
occupy the dxz, dyz or the dxy orbital.
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1.4 Hard and Soft Acids and Bases
Introduction
Irving-Williams series
Classification of acids and bases
Introduction
First, the distinction between Brnstead acids and bases and Lewis acids and
bases should be made clear:
Consider a simple transition metal complex, MLn. The central metal ion (a Lewis
acid) accepts an electron pair from each of the ligands (Lewis bases).
Irving-Williams Series
In 1953 Irving and Williams attempted to correlate stability constant data for the
group 2 metals. They looked at the stability constants for the M2+ ions of group 2
and some of the first transition series. They found that, for a given ligand (Lewis
base), the stability constants for the metal ion (Lewis acid) generally followed
the same sequence. This sequence became known as the Irving-Williams series.
Ba2+ < Sr2+ < Ca2+ < Mg2+ < Mn2+ < Fe2+ < Co2+ < Ni2+ < Cu2+ > Zn2+
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Crystal Field Theory (see Section 1.1) assumes that the interaction between
metal ions and surrounding ligands is completely electrostatic. Metal ions with
high charge densities interact strongly with the surrounding ligands, so it is
expected that the smaller metal ions form more stable complexes than the larger
metal ions. Copper is considered out of line with predictions based on Crystal
Field Theory. This is probably a consequence of the tendency for Cu(II) to form
distorted octahedral complexes.
The electrostatic argument would also predict the stability constants for M3+ to
be greater than those for M2+, due to increasing charge density. This is generally
the case.
In 1963 Pearson suggested that class a metal ions should be termed hard and
those of class b should be termed soft. This was extended to include ligands, so
that Lewis acids and bases can be classified as hard, soft or borderline. The term
borderline is introduced as the terms hard and soft are not absolute. There are
some species which fall in the middle, which will be classified as borderline.
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Examples of hard, soft and borderline acids and bases
The element highlighted in bold is that which is directly coordinated to the
metal
+ 3+ 4+ 2+ 3+
Fe2+, Co2+, Ni2+, Cu+, Ag+, Au+, Hg+, Hg2+, Pt2+,
H , Sc , Ti , Cr , Cr ,
Acids + 7+ 3+ 3+
Cu2+, Zn2+, Ru3+, Pd2+, all d-block metals in
Mn , Mn , Fe , Co
Ir3+ zero oxidation state
NH3, NH2R, OH2, OH-, O2- H-, R-, C2H4, C6H6, CN-, CO,
NH2Ph, N2, NO2-,
Bases , OR-, OR2, CO32-,SO42-, SCN-, PR3, P(OR)3, SR2, SHR,
SO32-, -
Br , SCN-
Pearson also stated that "hard acids prefer to coordinate to hard bases, and soft
acids to soft bases". This statement is still used today and is known as the HSAB
Principle. The word prefer is used as there are many examples of strong bonds
between mismatched pairs of acids and bases. This is due to the fact that there
are other factors (in addition to matching hard and soft acids and bases) that
affect the strength of bonds.
Question 1.4.1
What is a Lewis acid?
A. An electron acceptor
B. An electron donor
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2. UV-visible absorption spectroscopy
This section will include:
Example spectra
Explanation of key features of the
spectra
Using spectra to calculate values of o
Selection rules
Wavelengths of colours
and complementary colours
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Colour of light Wavelength Colour of light
absorbed ranges / nm transmitted
UV-Visible Spectrum of
[Ti(OH2)6]3+
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attributable to the absorption band at 493 nm. This absorption band is in the
visible region of the electromagnetic spectrum, so the complex is coloured.
Question
What colour will the complex be?
Calculation of o
If the wavelength of the light absorbed is known, the value of o can be
calculated by converting from wavelength to energy. The following two equations
are used:
E = h
where E is energy, h is Plank's constant and is frequency
c =
where c is the speed of light, is the wavelength and is the frequency
Therefore,
E = 6.626 x 10-34 x 2.998 x 108 / 493 x 10-9 Js ms-1 / m
E = 4.029 x 10-19 J
This is the value of o for one molecule of the complex. The value for one mole
can be calculated by multiplying by Avogadro's number, 6.022 x 1023 mol-1.
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Another common way to express the CFSE is in cm-1 (1 kJ/mol = 84 cm-1),
in this example about 20.400 cm-1 which corresponds to a wavelength of 490 nm.
You should be familiar with energy conversions (convert between kJ and kJ/mol
and cm-1 and wavelength in nm) !
Page 28 of 33
The absorption band for the d-d transition is broad
This is due to the fact that molecules are not static. The [Ti(OH2)6]3+ molecule is
continually vibrating and the Ti-O bond lengths are continually changing. The size
of o depends on the Ti-O bond length. If the Ti-O bonds are longer there is less
repulsion between the ligand lone pairs and the d-electrons, so o will be
smaller. At any one instant, there will be a range of Ti-O bond lengths in solution
and a range of o values. Hence the absorption band is broad.
There is a strong absorption in the UV region (to the left of the graph)
This is due to charge transfer transitions. This type of transition involves
electrons moving from orbitals which are essentially ligand in character to
orbitals which are essentially metal in character. This means charge transfer
from one part of the molecule to another takes place. This type of absorption
tends to be intense as there are no selection rules governing the transition.
Charge transfer transitions can also take place in the visible region of the
electromagnetic spectrum. When this happens, the complex is usually intensely
coloured. For example, the complex KMnO4 is a deep purple colour because
charge transfer transitions take place between O2- ligands and the Mn metal
centre (ligand metal charge transfer). Metal ligand charge transfer is also
possible.
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Selection rules
Electronic transitions are subject to selection rules. These selection rules are
statements about whether a given transition is allowed or forbidden. If the
transition obeys a given set of rules it is said to be allowed, if it does not follow
the rules it is said to be forbidden.
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2. Laporte selection rule
Terminology:
Gerade (g)
An orbital which possesses a centre of symmetry
Ungerade (u)
An orbital which does not possess a centre of symmetry
The subscript g in the t2g and eg indicates that the orbitals have a centre of
symmetry in an octahedral field. In a tetrahedral field there is no centre of
symmetry, so the subscript g's are removed.
The Laporte selection rule (also known as the symmetry selection rule) states
that for a complex that contains a centre of symmetry only transitions which
involve a change in parity are allowed. That is, only transitions between g and u
orbitals are allowed.
gerade-ungerade gerade-gerade ungerade-ungerade
Allowed Forbidden Forbidden
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Calculation example for Ruby (Cr3+)
From:
http://chemwiki.ucdavis.edu/Inorganic_
Chemistry/Crystal_Field_Theory/Virtual%
3a_Electronic_Structure/Energy_Level_S
plitting
In most compounds, there are large gaps in energies between the bonding
orbitals (which are typically filled with electrons) and the antibonding orbitals
(which are typically empty). Promotion of an electron from an occupied bonding
orbital to an unoccupied antibonding orbital (a * transition) usually requires
6 eV or more energy. Such light falls in the ultraviolet region, which the human
eye cannot detect, and the substance is colorless. Nonbonding orbitals (which are
usually occupied) lie between the bonding and antibonding orbitals and thus give
rise to lower energy transitions. These n * transitions are usually 3.5 eV or
greater, which still corresponds which light in the ultraviolet region (near
ultraviolet light).
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In order to have color, a substance must have an electronic transition whose
energy change is between 1.8 and 3.1 eV, which corresponds with light in the
visible range (about 400 to 700 nm). Such low energy transitions require closely
spaced energy levels, some of which contain electrons and some of which do not.
Many dyes are large organic molecules with extended bonding, which gives rise
to closely spaced occupied and unoccupied * orbitals. Transition metal
complexes are often colored, because the crystal field splitting gives rise to
closely spaced, partially filled d orbitals.
For the Inorganic Chemistry Exam, please study especially the chapters about
Crystal Field Theory and CFSE as well as UV/VIS spectroscopy.
The HSAB principle, Jahn-Teller Effect and Spin-selection rules are more
advanced subjects and will be covered later in more detail.
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