What Should a Bonding Theory Explain?

In our intro have already outlined some of the properties of transition metal
complexes. For a bonding theory to be effective it must address these points.

You already have some understanding of Lewis structures and VSEPR theory….
They don’t fit the bill.
Where do they fall down?
I. Colours of Transition Metal Complexes
Why are most transition metal complexes brightly coloured but some aren't?
Why do the colours change as the ligand changes?
Why do the colours change as the oxidation state of the metal changes,
even for complexes of the same ligand?
 What Should a Bonding Theory Explain?
The Magnetic Moment of a Complex and the Number of Unpaired Electrons

How can we determine the number of unpaired electrons…..

This is important before we define our theory of bonding.

Increasing field strength

Cobalt(II) chloride hexahydrate

3 unpaired electrons which align their spins with a large
applied magnetic field and are drawn into it.
For a more complete discussion on magnetism see R-C p. 14-15

paired e- unpaired e-
 Handling magnetic data
One approach is to use a Gouy balance is used to measure the mass of a sample with
and without being exposed to a strong magnetic field.

The difference in mass can be used to calculate the magnetic susceptibility of the
sample, and from the magnetic susceptibility the magnetic moment can be obtained.

(note: M is the molar susceptibility and is the mass

susceptibility (g) multiplied by the molecular mass M.)

Where does the magnetic moment come from?

 Molecular magnetic moment
The magnetic susceptibility and thus the magnetic moment are due to moving charges.
Just like the coil of wire on the previous transparency.

In an atom, the moving charge is an electron

For first row transition metals, the affect of the orbital magnetic moment is
negligible.

This means that the measured magnetic moment can be directly related to the
number of unpaired electrons (n) in the ion. This value is called the spin-only
magnetic moment, and its units are Bohr Magnetons (B.M.).
 Magnetic questions for our model.
Why do different complexes of the same metal ion in the same
oxidation state have different numbers of unpaired electrons?

For example Fe3+, Co3+, and Ni2+

FeCl3.6H2O K3[Fe(CN)6]
= 5.9 B.M.; 5 unpaired electrons = 1.7 B.M.; 1 unpaired electron

K3[CoF6] [Co(NH3)6]Cl3
= 4.9 B.M.;4 unpaired electrons  = 0; no unpaired electrons

[Ni(NH3)6]Cl2 K2[Ni(CN)4]
= 2.8 B.M.; 2 unpaired electrons  = 0; no unpaired electrons

Why are there only certain values of the number of

unpaired electrons for a given metal ion?

For example, complexes of Fe(II) and Co(III) can only have

zero or 4 unpaired electrons, never two. Complexes of Fe(III)
can only have 5 unpaired electrons or 1 unpaired electron.

Why are Ni2+ complexes, all octahedral complexes have 2

unpaired electrons but square planar complexes are
diamagnetic (no unpaired electrons)?
Coordination numbers and geometry
Why do some transition metal ions seem to have a fixed
coordination number and geometry, while other metal ions seem
variable?
Cr3+ : practically always 6-coordinate, octahedral

Co3+ : practically always 6-coordinate, octahedral

Co2+ : both 6-coordinate octahedral and 4-coordinate

tetrahedral complexes known

Ni2+ : octahedral and square planar complexes common;

some tetrahedral complexes known

Ni4+ : only octahedral complexes known

Pt2+ : practically always square planar

 Reactivity
Why do some metal complexes undergo ligand-exchange reactions very rapidly and other
similar complexes react very slowly, yet this reaction is thermodynamically favorable?

[Co(NH3)6]3+ + 6H3O+ [Co(H2O)6]3+ + 6NH4+

The equilibrium constant for this reaction is approximately 1025, and yet an acidic solution of the
hexamminecobalt(III) ion requires several days before noticeable change occurs.

But, the reaction of the corresponding copper(II) complex proceeds instantaneously.

[Cu(NH3)6]2+ + 6H3O+ [Cu(H2O)6]2+ + 6NH4+

Why are the chemistries of Co3+, Pt2+, Cr3+, and Pt4+ so broad with numerous examples of
known, characterized, structural and geometric isomers and yet other transition metal ion
chemistry is seemingly limited?

There are three isomers of CrCl3.6H2O that have been isolated and characterized. ([Cr(H2O)6]Cl3,
[Cr(H2O)5Cl]Cl2.H2O, and [Cr(H2O)4Cl2]Cl.2H2O).

Why is there no interconversion to the most stable compound?

Why doesn't FeCl3.6H2O have any isomers?

Why doesn't cis-[Pt(NH3)2Cl2] convert readily to trans-[Pt(NH3)2Cl2]?

 Course Outline
I. Introduction to Transition Metal Complexes.
Classical complexes (Jorgenson and Werner)
Survey of ligand coordination numbers, geometries and types of ligands
Nomenclature
Isomerism
II. Bonding in Transition Metal Complexes.
Electron configuration of transition metals
Crystal field theory
Valence bond theory
Simple Molecular Orbital Theory
Electronic Spectra and Magnetism
III. Kinetics and Mechanisms of Inorganic Reactions.
Stability and lability
Substitution reactions
Electron transfer reactions
IV. Descriptive Chemistry of TMs.
V. Organometallic Chemistry
18 e- rule, , and  bonding ligands (synergistic bonding)
Metal carbonyls, synthesis, structure, reactions
Compounds with delocalized -conjugated organic ligands.
Reactions and catalysis
 Crystal Field Theory
At roughly the same time that chemists were developing the valence-bond model for
coordination complexes, physicists such as Hans Bethe, John Van Vleck, and Leslie
Orgel were developing an alternative known as crystal field theory (CFT).

CFT tries to describe the influence of the electrical field of neighboring ions on the
energies of the valence orbitals of an ion in a crystal.

Crystal field theory was developed by considering two compounds: manganese(II)

oxide, MnO (octahedral), and copper(I) chloride, CuCl (tetrahedral).

MnO
Each Mn2+ ion is surrounded by 6
O2- in an octahedral geometry.
This serves as a model for
transition metal complexes with 6
ligands surrounding it.

What happens to the energies of the orbitals on an

Mn2+ ion when this ion is buried in an MnO crystal?
 CFT cont’d
4s and 4p
Although repulsion between electrons
will likely occur between electrons in
these orbitals and the electrons on the
six O2- ions surrounding the metal ion in
MnO and increase the energies of these
orbitals. These orbitals will remain
degenerate (have the same energy).

Why?
 CFT cont’d
3d What is different about the d-orbitals?

Assume the six O2- ions

surrounding each Mn2+ ion
define an XYZ coordinate
system.

Two of the 3d orbitals on

the Mn2+ ion point directly
toward the six O2- ions

The other three orbitals lie

between the O2- ions
 Affects on d-orbital energies
As with the energy of the 4s and 4p orbitals, the energy of the five 3d orbitals increases
when the O2- ions are brought close to the Mn2+ ion.

Differences arise because and the energy of the 3dx2-y2 and 3dz2 increases much more
than the energy of the 3dxy, 3dxz, and 3dyz.

As a result of the crystal field of the six O2- ions in MnO the degeneracy of the five 3d
orbitals is split.
 Affects on d-orbital energies
(a more general case)

Consider a general first row TM, Mn+ with an unspecified number of d-electrons.

2e-
e- e- e-
e- e- 2e- 2e-
Mn+ 12e-
e- Mn+ e-
e- e- 2e- 2e-
e- e-
2e-

Barycenter

degenerate
d-orbitals Mn+
surrounded
eg
Increased in energy
degenerate by 6 ligand
because of e-e interactions
e- pairs at a
o
d-orbitals
distance rM-L t2g
Electostatic interaction between M and electrons are neglected Mn+
e- pair interaction
considered
 Crystal Field Splitting
vs.
Electron Pairing Energies
Start with two nondegenerate valence electronic energy levels.

What happens if we put 2 electrons into these orbitals?

E2 E2

Increasing  What about the second


Energy electron?
e-
E1 E1
Insert 1 electron. It
goes into the lowest
energy level.

There are two cases that must be considered.

 Low Spin vs. High Spin
This is similar to what you saw in 331 for filling of d-orbitals.
Energy is required to pair electrons in the E1 energy level.
e- Case II
E2 (Weak field, high spin)
This is preferred when
  < paring energy. The
total energy for the
e- process is Enet=E1+E2
E2 E1 = 2E1 +.
Increasing
Energy

e-
E1 E2
Case I
(Strong field, low spin)
This is preferred when
  > paring energy. The
total energy for the
process is Enet=2E1+P.
e- e- E1
 Crystal Field Stabilization Energies
What happens when this is applied to degenerate orbitals similar to
that seen for energy levels of a metal within an octahedral field?

For d1, d2, d3 there is no choice

Octahedral Geometry where the electrons are placed.
dx2-y2, dz2
eg
This is also the case for d8, d9, d10.
3/5 o
o The questions arise for d4, d5, d6, d7.
2/5 o
t2g How can we understand what configuration is assumed?
dxy, dyz, dxz

d4 d5
or …
t2g eg t2g eg t2g eg t2g eg
 Crystal Field Stabilization Energies
How are they calculated?

dx2-y2, dz2 d6-High Spin

eg

3/5 o t2g eg
o
2/5 o CFSE = 4(2/5 o )-2(3/5 o)
t2g = 2/5 o
dxy, dyz, dxz

d6-Low Spin
The Reference Unsplit System
?
t2g eg

Has 1 “paired set” of electrons. CFSE = 6(2/5 o )-2P

= 12/5 o-2P
 Which configuration will occur?

d6-High Spin d6-Low Spin

t2g eg t2g eg

CFSE = 4(2/5 o )-2(3/5 o) CFSE = 6(2/5 o )-2P

= 2/5 o = 12/5 o-2P
= 12/5 o- 2o

The difference between the energy of the two configurations is

relative to the differences between o and P.

Hence,

If o > P the low-spin case has greater CFT stabilization energy.

If o < P the high-spin case has greater CFT stabilization energy.

Similar results are seen in similar analysis of d4, d5, and d7.
Tetragonal Octahedral and Square Planar Fields

2e-
2e-
2e- 2e- 2e- 2e-
2e- 2e-
2e- 2e- 2e- 2e-
2e- 2e-
2e-

2e-
Octahedral field Tetragonally Square planar
elongated field
octahedral field
Try Assignment #2
dx2-y2, dz2
eg Question #6

o

t2g
dxy, dyz, dxz
 Tetragonally Distorted Field
2e-
2e-
2e- 2e-
2e- 2e-
elongation in the z-direction
2e- 2e-
2e- 2e-
2e-

2e-
Octahedral field Tetragonally
elongated
octahedral field
dx2-y2, dz2 dx2-y2
dz2

o
dxy

dxy, dyz, dxz

dyz, dxz
 Understanding the energy changes for
the tetragonal distortion
2e- When elongation occurs in the z-direction,
simultaneous contraction in the x- and y-
direction results from the availability of space
2e- 2e- around Mn+.
The coulombic attraction between the
2e- 2e- ligan electrons and the charge of the
metal center pulls the ligand closer.

2e- What about orbital energy changes?

The barycenter remains constant.
dx2-y2, dz2 dx2-y2
Orbitals with a “z” component
dz2 become more stable.

o Why?…..it’s electrostatics.
dxy
Orbitals with “ x and y”
dxy, dyz, dxz components become less
dyz, dxz
stable.
A summary of the effects on the orbital energies.

The dx2-y2 orbital is increased in energy because it is

directed toward the x- and y- ligands which have
approached the M center more closely.

dx2-y2
The dz2 orbital is decreased in energy because it
is directed toward the retreating z- ligands. The dz2
change in energy of the dz2 orbital is greater than
the dyz and dxz because it is directed the
elongated positions.
dxy
The dxy orbital is increased in energy
because it is directed toward the x- and y-
ligands which have approached the M dyz, dxz
center more closely. This results in more
e-e repulsion between e in the d-orbital
and on the ligands.
The dyz and dxz orbitals are decreased in energy because
they feel direct influence of the retreating z- ligands. The
change in energy of the dz2 orbitals is greater than that seen
for the dyz and dxz orbitals because it is directed at the
elongated positions.
 Square Planar Field.
Question #6 on Assignment #2 deals with the Square planar field.
It is YOUR responsibility to apply the approach we have to this system.

A couple of important things to note:

The square planar geometry is an octahedral field with NO z-ligands.

You cannot assume the Barycenter is constant. Why might this be?

Significant stabilization of metal orbitals with z components occurs.

Good Luck!
 Tetrahedral Field.
z

y
Mn+

It is difficult to visualize the tetrahedral field and the d-orbitals together.

The tetrahedral field can be viewed as ligands at vertices of a cube.

 Tetrahedral field and d-orbitals
z

The key to understanding the orbital ordering is the

distance the d-orbitals are from the approaching ligands.
x
This is because none of the d-orbitals point directly at the
incoming ligands.

It is useful to to relate the distance

of the tip of the d-orbitals from the
incoming ligands in terms of the
edge dimension (L) of the cube.

The dxy, dyz, and dxz orbitals are L/2 away from the ligands whereas dx2-y2 and dz2 are L√2/2 away.
 Orbital ordering in a tetrahedral field
The dxy, dyz, and dxz orbitals are L/2 away from the ligands whereas dx2-y2 and dz2 are L√2/2 away.

The closer the orbitals are to the ligands the greater

the interaction…and greater the increase in energy.

dxy, dyz, dxz

t2g
A useful point to remember is,
Barycenter 2/5 T because of the LESS CLEAR-CUT
T distinction between orbital
3/5 T interactions the splitting of the d-
orbitals in a tetrahedral field is
dx2-y2, dz2 about half that observed for an
eg
octahedral field.
 TMs and Colour:
Electronic Absorption Spectroscopy.

Where does the colour come from?

 Sources of Colour in TM Complexes
dx2-y2, dz2 dxy, dyz, dxz
eg

3/5 o Barycenter 2/5 T

Barycenter o T
2/5 o 3/5 T
t2g
dx2-y2, dz2
dxy, dyz, dxz eg

Octahedral Geometry Tetrahedral Geometry

The colours of TM complexes arise from the absorption of light.

This absorption of light results in d  d transitions. (movement of the electrons)

G.S E.S
For [Ti(OH2 )]3+
eg eg o = hv
hv = 20 300 cm-1
d? o o = 493 nm
= 243 kJ/mol
t2g t2g
 Aspects of Colour
The Type of Colour.

This depends on the position of the absorption band(s); this is a fancy way
to say the difference in the energy of the d-orbitals.

The INTENSITY of Colour.

This depends on how strongly (or weakly) the light is absorbed. This is
outlined by Beer’s Law. ( = the absorption coefficient; A= cl)

i) d  d transitions are formally forbidden….. Why?

Yet the still occur but they are not intense absorptions.

d  d bands when molecules don’t have a center of symmetry tend to be stronger.

ML4(tet) >  ML6(oct)

ii) Any transition that involves the change of the d-electron spin is forbidden.
We often speak of “spin-allowed” and “spin-forbidden” transitions.
 Light …. IT’S ENERGY!
The Electromagnetic Spectrum.

absorption

The Artists Colour Wheel.

We can determine the colour of a

compound from the light it absorbs.
Complimentary colours are on
opposite sides of the wheel.
apparent colour
 How many transitions?
G.S E.S
For [Ti(OH2 )]3+
eg eg o = hv
hv = 20 300 cm-1
d1 o o = 493 nm
= 243 kJ/mol
t2g t2g

t2g1 eg1

The absorption of visible light promotes the t2g electron to the eg.

The energy of the light corresponds to o. This is because there is only one possible transition.

Do we see only ONE absorption if we have ONE d-electron?

At first glance this may appear true….but is it?

 dn Transitions
We must remember that any d  d transitions observed are “spin-allowed”.

This means that in such a dn configuration you will observe as many E.S.s as
is possible as long as the spin of the electron doesn’t change.
G.S E.S E.S

eg hv eg eg

d1 o o o
t2g t2g t2g

G.S E.S. #1 E.S.#2

eg hv eg eg

d2 o o o
t2g t2g t2g

E.S.#1 is of lower energy than E.S.#2

 Energies of Transitions.
G.S E.S. #1 E.S.#2

eg hv eg eg

d2 o o o
t2g t2g t2g

E.S.#1 is of lower energy than E.S.#2

But there are three absorptions!!! WHY?

The highest energy transition corresponds to the promotion of both electrons.

G.S E.S. #3

eg hv eg

d2 o o
t2g t2g
 What about other dn systems?
G.S E.S.

eg hv eg
HS d6 OCT o ? o
t2g t2g
Should we see one or two transitions?

G.S E.S.

eg hv eg
HS d4 OCT o ? o
t2g t2g

G.S E.S.

eg hv eg
d9 OCT o ? o
t2g t2g
What governs the magnitude of ?
1. The identity of the metal.
CFS of 2nd row TMs is ~50% greater than 1st row.
CFS of 3rd row TMs is ~25% greater than 2nd row.

There is also a small increase in CFS along each period.

2. The Oxidation State of the metal.

Generally, the higher the oxidation state of the metal the

greater the splitting. This explains why Co(II) complexes are
H.S. and most Co (III) complexes are L.S.

3. The Number of Ligands.

This was already hinted at when we looked at Tetrahedral vs.

Octahedral splitting. In this case the T ~ 4/9 O.

4. The nature of the ligands.

 Invisible Ink
heat
2[Co(H2O)6]Cl2(s) Co[CoCl4](s) + 12 H2O

Why does this happen?

Spectrochemical Series
The splitting of d orbitals in the crystal field model not only depends on the geometry of the
complex, it also depends on the nature of the metal ion, the charge on this ion, and the
ligands that surround the metal.

When the geometry and the ligands remain constant, splitting decreases in the following order:
Pt4+>Ir3+>Rh3+>Co3+>Cr3+>Fe3+>Fe2+>Co2+>Ni2+>Mn2+
strong-field ions weak-field ions

When the geometry and the metal are held constant, splitting of the d orbitals decreases in
the following order:

CO~CN-> NO2->NH3>-NCS->H2O>OH->F->-SCN-~Cl->Br-
strong-field ligands weak-field ligands
 Hydration Enthalpies
A success of CFT.

Mn+(g) + 6H2O(l) [M(OH2)6]n+(aq)

What do you expect?

What would you use to predict the trend across the period?

Hohydration (MJ.mol-1)

Ca2+ Ti2+ V2+ Cr2+ Mn2+ Fe2+ Co2+ Ni2+ Cu2+ Zn2+

How can we use CFT to understand this?

 CFT and Hydration Enthalpies

Hohydration (MJ.mol-1)

Ca2+ Ti2+ V2+ Cr2+ Mn2+ Fe2+ Co2+ Ni2+ Cu2+ Zn2+

The more exothermic hydration enthalpy is the result of

the CFSE which may be determined as a fraction of .
dx2-y2, dz2
eg The only exceptions are
d0, d5 H.S. and d10.
3/5 o WHY?
o
2/5 o NOTE. On p.438 of R.C. all stabilization
t2g energies are noted as negative.
THIS IS NOT CORRECT!
dxy, dyz, dxz
Do similar observations appear elsewhere?

Lattice energies of MCl2.

MX interatomic distances for transition metal halides.

Ionic radii for divalent TM cations. (3d series)

The same explanation

used for hydration
energies can be applied
to these systems.
 Spinel Structures.
CFT aids in understanding the arrangements of metal ions in spinel
structures (R.C. Chpt.12).

READ RODGERS WHERE SPINEL STRUCTURES

ARE OUTLINED IN DETAIL. (p. 182-185).

The spinel is a MIXED METAL OXIDE with a general formula

(M2+)(2M3+)(O2-)4..

Spinel is MgAl2O4

Many compounds adopt this type of structure.

The basic structure is a FCC lattice of O2- anions.

Cations occupy tetrahedral and octahedral holes.

How does CFT help us understand this structure?

 Spinel structures and CFT
Normal Spinal Structure.
M2+ is tetrahedral, M3+ is octahedral Example: (Mg2+)T(2Al3+)O(O2-)4

Inverse Spinal Structure.

M2+ is octahedral M3+ is tetrahedral and in the remaining octahedral holes
Example: (Fe3+)T(Fe2+,Fe3+)O(O2-)4
This later example is magnetite or Fe3O4.

Fe3O4 (Fe2+, 2Fe3+, 2O2-)

Note the O2- is a weak field ligand. (Fe is H.S.) Fe0 is d8

What are the electron configurations of the Fe ions?
dxy, dyz, dxz
Fe2+ dx2-y2, dz2
eg
2/5 T
3/5 o OR
o T
3/5 T
2/5 o
t2g
dx2-y2, dz2
dxy, dyz, dxz eg
 Mn3O4 Spinel Structure.
Mn3O4 (Mn2+, 2Mn3+, 4O2-)
Electron configurations are ….. ?

dxy, dyz, dxz

dx2-y2, dz2
eg
2/5 T
3/5 o OR
o T
3/5 T
2/5 o
t2g
dx2-y2, dz2
dxy, dyz, dxz eg
 How does CFT measure up?
I. Colours of Transition Metal Complexes
Why are most transition metal complexes brightly coloured but some aren't?
Why do the colours change as the ligand changes?
Why do the colours change as the oxidation state of the metal changes,
even for complexes of the same ligand?

II. Why do different complexes of the same metal ion in the same oxidation state
have different numbers of unpaired electrons?

Why are there only certain values of the number of unpaired

electrons for a given metal ion?

III. Why do some transition metal ions seem to have a fixed coordination
number and geometry, while other metal ions seem variable?

IV. Why do some metal complexes undergo ligand-exchange reactions

very rapidly and other similar complexes react very slowly, yet this
reaction is thermodynamically favorable?
 Course Outline
I. Introduction to Transition Metal Complexes.
Classical complexes (Jorgenson and Werner)
Survey of ligand coordination numbers, geometries and types of ligands
Nomenclature
Isomerism
II. Bonding in Transition Metal Complexes.
Electron configuration of transition metals
Crystal field theory
Valence bond theory
Simple Molecular Orbital Theory
Electronic Spectra and Magnetism
III. Kinetics and Mechanisms of Inorganic Reactions.
Stability and lability
Substitution reactions
Electron transfer reactions
IV. Descriptive Chemistry of TMs.
V. Organometallic Chemistry
18 e- rule, , and  bonding ligands (synergistic bonding)
Metal carbonyls, synthesis, structure, reactions
Compounds with delocalized -conjugated organic ligands.
Reactions and catalysis