CHEM1000 Workshop 4.

2 S1, Week 11, 2017

Activity 4.2: Electronic structure of complexes

Why?
Coordination compounds exhibit characteristic magnetic and colour properties. These properties arise from
the energy splitting of the transition metals d orbitals caused by the presence of ligands surrounding the
metal in a complex. It is important to recognise which d orbitals are occupied by electrons, as the pattern of
this occupation determines the magnetic properties and colour of the compound. These properties are often
used as a tool to understand the bonding in coordination compounds and to tailor compounds with useful
magnetic and optical characteristics.

Learning Objectives
Understand from Crystal Field Theory how occupation of d orbitals is no longer degenerate and how they
split in energy as a result of d orbitalligand interactions in octahedral and tetrahedral fields.

Relate the energy difference between the two sets of d orbitals to the crystal field splitting parameter, ,
and correlate its magnitude to the magnetic properties of transition metal complexes.

Resources
Blackman, Bottle, Schmid, Mocerino & Wille, Chemistry, Chapter 13.4, pp 531534.

Model 1: Crystal field model for an octahedral complex

According to the crystal field model, the splitting of the d orbitals is a function of the relative positions of
the ligands and the individual d orbitals of the metal centre. If we align the metal centre at the origin and
the ligands in an octahedral geometry along the x-, y- and z- axes they can be positioned relative to the d
orbitals of the transition metal.

Critical Thinking Questions

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CHEM1000 Workshop 4.2 S1, Week 11, 2017
1. Draw the Cartesian x-, y- and z-axes on each of the d orbital diagrams in Model 1 and verify the
orbital labels. The orbitals are all in the same relative orientations. Use the Cartesian axes on the first
d orbital as a guide.

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Activity 4.2: Electronic structure of
complexes
2. Which d orbitals lie along the x-, y- or z-axes and which lie between any two axes?

3. Which d orbitals experience a direct end-on-end interaction with ligands that also lie along the axes?

4. Which d orbitals do not experience a direct end-on-end interaction with the ligands?

5. Based on your answers to CTQs 3 and 4 divide the five d orbitals into two sets and explain your
reasoning.
Set 1 Set 2

6. From CTQ5, electrons in which set of orbitals do you think will experience the stronger repulsion with
the electron-rich ligands due to end-on-end overlap of orbital lobes? Explain the reason for your
choice.

7. The diagram below shows all five degenerate d orbitals in a theoretical spherically symmetrical ligand
field (in the absence of localised ligands). In an octahedral crystal field the energies of the two sets of
orbitals depends on the extent of repulsion with the ligands. Complete the diagram below by drawing
the two sets of d orbitals in the octahedral field, labelling each one.
Model 2: Crystal field model for a tetrahedral complex
As for the octahedral field, we can split the d orbitals as a function of the relative positions of the ligands in
a tetrahedral complex and the individual d orbitals. If we align the metal centre at the origin and the
ligands in a tetrahedral geometry at the edges of the cube (green spheres = positions of ligands) they can
be positioned relative to the d orbitals of the transition metal.

Critical Thinking Questions

8. Draw the Cartesian x-, y- and z-axes on each of the d orbital diagrams in Model 2 and verify the
orbital labels. The orbitals are oriented the same way as in Model 1. The ligands in the tetrahedral
complex are placed at opposite corners of a cube surrounding the metal centre.
9. How have the positions of the d orbitals changed relative to the ligand positions from the octahedral to
tetrahedral ligand field? (hint: count the direct end-on-end interactions for both geometries)

10. In Model 2, which d orbitals are observed to have most of their electron density at the edges of the
cube (i.e. which d orbitals are closest to the ligands)?

11. In Model 2, which d orbitals are observed to have most of their electron density at the faces of the
cube?
12. Based on your answers to CTQs 10 and 11 divide the five d orbitals into two sets and explain your
reasoning.
Set 1 Set 2

13. In a tetrahedral field no d orbitals experience a direct end-on-end interaction with the ligands.
However, from CTQ12 electrons in which set of d orbitals do you think will experience the stronger
repulsion with the electron-rich ligands? Explain the reason for your choice.

14. The diagram below shows all five degenerate d orbitals in a free metal ion or barycentre, i.e. in the
absence of localised ligands. In a tetrahedral ligand field the energies of the two sets of orbitals
depends on the extent of repulsion with the ligands. Complete the diagram below by drawing the two
sets of d orbitals in the tetrahedral field, labelling each one.

15. What is the relationship between the relative energies of the two sets of d orbitals in the tetrahedral
and octahedral ligand fields?

16. How does the relationship between their relative energies relate to their ligand field splitting energies
(O for octahedral and T for tetrahedral)? Ligand field splitting energy is the difference in energy
between the two sets of atomic orbitals on the metal centre.
Model 3: Effect of different ligands on the magnitude of O

The energy between the two sets of d orbitals is called the crystal
field splitting parameter (). The magnitude of is heavily dependent on the identity o

weak field
4 unpaired electro

Fe2+
free ion
4 unpaired electrons

paramagnetic

paramagnetic

Increasing
I Br Cl F OH OH2 NH
O

Critical Thinking Questions

17. Which ligand shown in Model 3 has:
a) the largest crystal field effect?

b) the smallest crystal field effect?

18. What is the difference, as shown in Model 3, between the ways the electrons fill the d orbitals in the
weak field complexes and in the strong field complexes?

19. Since electrons fill orbitals to produce the lowest energy state, why do you think electrons are
unpaired in the free atom and weak field complexes but are paired up in the strong field complexes?
Consider the relative magnitudes of O and the repulsive pairing energy in your answer.

20. Since a magnetic field is associated with electron spin with the polarity determined by the value of ms
(spin quantum number), why do you think the weak field case shown in Model 3 is paramagnetic and
the strong field case is diamagnetic?

21. Explain why weak field complexes are sometimes called high spin and strong field complexes are
sometimes called low spin.

22. The order of the ligands along the x axis in Model 3 is called the spectrochemical series. Suggest a
reason why this is so. If you cannot suggest a reason for this now, then skip this question for now
and come back to it after completing Model 5.

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Model 4: Magnetic moment
The magnetic moment () can be determined by measuring the torque experienced in an external magnetic
field. The unit for the magnetic moment caused by the spin or angular momentum of electrons is the Bohr
magneton (B). The magnitude of the magnetic moment depends on the number of unpaired valence
electrons, n, and can be estimated by the following equation:

= n(n+2) B

The magnetic moments of a series of octahedral complexes were measured and are given in the table below.
These complexes are of the form [ML6]x+, where M is a metal, L is a monodentate ligand, and x is the formal
charge of the complex sphere.

Ligand (L) / Magnetic moment (in Bohr magnetons)

d electron Metal ion
config (M)
Cl OH2 NH3 CN
3
3d 3+ = 3.85 B = 3.85 B = 3.85 B = 3.85 B
Cr
5
3d 3+ = 5.90 B = 5.90 B = 5.90 B = 1.73 B
Fe
6
3d 2+ = 4.90 B = 4.90 B = 4.90 B = 0.00 B
Fe
8
3d 2+ = 2.81 B = 2.81 B = 2.81 B = 2.81 B
Ni

Critical Thinking Questions

23. Calculate the number of unpaired electrons in each case given in Model 4. Sketch diagrams
illustrating the electron occupation in an octahedral field for each of the six cases. The first one has
been completed for you.

3d3 3.85 B 3d5 5.90 B 3d5 1.73 B 3d6 4.90 B 3d6 0.00 B 3d8 2.81 B

n=3

24. For each of the complexes given in Model 4:

a) identify the paramagnetic complexes.

b) identify the diamagnetic complexes.

25. For each of the complexes given in Model 4:

a) identify the low spin complexes.

b) identify the high spin complexes.

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26. Which ligand(s) are:
a) more likely to induce a low spin complex?

b) less likely to induce a low spin complex?

27. Based on your answer to CTQ 26 how does the ligand position in the spectrochemical series relate to
the likelihood of the complex being low spin?

28. Which ligand (other than CN) is also likely to give low spin complexes where possible? Hint: refer to
Model 3.

29. Why do the chromium(III) and nickel(II) complexes all have the same electron configuration and thus
spin state regardless of the magnitude of O?

30. Calculate the likely magnetic moments (in Bohr magnetons) for the following pairs of complexes:
a)
[Cr(OH2)6]2+ and [Cr(OH2)6]3+

b) [Fe(OH2)6]3+ and [Fe(CN)6]3

 Activity 4.2: Electronic structure of
complexes
31. How many unpaired electrons are there likely to be if:
a) the magnetic moment was measured as 5.91 B?

b) a d7 octahedral complex has a low spin configuration?

32. What spin state are the following complexes likely to be in:
a) a d4 tetrahedral complex with a magnetic moment of 0 B?

b) an octahedral complex of iron(II) that is found to be diamagnetic?

Model 5: Perceived Colour of complexes

Metal and Oxidation Ligand UV-visible absorption maximum Perceived Colour
State wavelength ( max, nm)
Fe3+ Br- 640 Violet
Zn2+ CN- No absorption peaks due to complex Colourless
Co2+ Br- 700 Green/blue
Co2+ CN- 400 Yellow
Sc3+ Br- No absorption peaks due to complex Colourless

Consider the table above and answer the questions below.

33. What are the d orbital configurations for the metals listed above?

34. What d orbital configuration do the metals have that show no colour?
Activity 4.2: Electronic structure of
35. Looking at the cobalt complexes which ligand has the higher energy transition? Hint: Recall that in the
complexes
electromagnetic spectrum wavelength and energy are inversely proportional.

36. Is this a weak or strong ligand?

37. Using the colour wheel below, what is the relationship between the perceived colour and the absorption
maximum?
Activity 4.2: Electronic structure of
complexes
Homework problems
1. Use sketches of their boundary surfaces to explain why the dxz and dz2 orbitals have different energies
in octahedral coordination complexes. Explain what happens to their relative energies in a tetrahedral
or square planar complex.
2. (Extension question not examinable). Imagine a pentagonal bipyramidal complex (illustrated
below). How would the five d orbitals split as a result of the seven coordinate ligand field?

3. (Extension question not examinable). Consider the complex [Cr(OH2)4Cl2] illustrated below. A
regular octahedral structure is rarely found for this complex and it is often distorted to give the
structure on the right, where the water molecules laying on the xy-plane have moved closer to the
metal somewhat and the two chloride ions along the z-axis have moved further away. This is called a
tetragonal geometry. What effect will this distortion have on the splitting pattern of the d orbitals?
Use a sketch of the splitting pattern, similar to CTQs 7 or 14, to illustrate your answer.

4. The energy of photons in the visible region of the spectrum is roughly the same as the ligand field
splitting parameter . Recall that wavelength and energy are related through the following equation:

a) Using this information arrange the following three Cr(III) complexes in order of increasing
energy of the photons absorbed:
[CrF6]3 absorbs light in the region 500 560 nm
[Cr(OH2)6]3+ absorbs light in the region 480 500 nm
[Cr(NH3)6]3+ absorbs light in the region 435 480 nm
b) How does this relate to the order of ligands given in Model 3?
Activity 4.2: Electronic structure of
complexes
5. The coordination compound [Ni(OH2)6]Cl2 is green (absorbs red light). The coordination compound
[Ni(NH3)6]Cl2 is purple (absorbs yellow green light).

a) Which compound absorbs light with the shorter wavelength?

b) Which compound has the larger ligand field splitting of the d orbitals?
c) Which ligand produces the stronger field?

6. The electron in the d orbital of [Ti(OH2)6]3+ absorbs light at 570 nm in going from the lower energy
t2g orbital to the higher energy eg orbital.

a) Draw a diagram showing the electron transition that gives rise to this colour.
b) What colour is absorbed in this process and what is the perceived colour of a solution of this
complex?