1. Home
  2. Chemistry
  3. Transition metals and coordination
  4. Spectroscopic and magnetic

19.3 Spectroscopic and magnetic properties of coordination compounds

<< Chapter < Page
  Chemistry     Page 1 / 17
Chapter >> Page >
By the end of this section, you will be able to:
  • Outline the basic premise of crystal field theory (CFT)
  • Identify molecular geometries associated with various d-orbital splitting patterns
  • Predict electron configurations of split d orbitals for selected transition metal atoms or ions
  • Explain spectral and magnetic properties in terms of CFT concepts

The behavior of coordination compounds cannot be adequately explained by the same theories used for main group element chemistry. The observed geometries of coordination complexes are not consistent with hybridized orbitals on the central metal overlapping with ligand orbitals, as would be predicted by valence bond theory. The observed colors indicate that the d orbitals often occur at different energy levels rather than all being degenerate, that is, of equal energy, as are the three p orbitals. To explain the stabilities, structures, colors, and magnetic properties of transition metal complexes, a different bonding model has been developed. Just as valence bond theory explains many aspects of bonding in main group chemistry, crystal field theory is useful in understanding and predicting the behavior of transition metal complexes.

Crystal field theory

To explain the observed behavior of transition metal complexes (such as how colors arise), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory    (CFT). It allows us to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.

CFT focuses on the nonbonding electrons on the central metal ion in coordination complexes not on the metal-ligand bonds. Like valence bond theory, CFT tells only part of the story of the behavior of complexes. However, it tells the part that valence bond theory does not. In its pure form, CFT ignores any covalent bonding between ligands and metal ions. Both the ligand and the metal are treated as infinitesimally small point charges.

All electrons are negative, so the electrons donated from the ligands will repel the electrons of the central metal. Let us consider the behavior of the electrons in the unhybridized d orbitals in an octahedral complex. The five d orbitals consist of lobe-shaped regions and are arranged in space, as shown in [link] . In an octahedral complex, the six ligands coordinate along the axes.

This figure includes diagrams of five d orbitals. Each diagram includes three axes. The z-axis is vertical and is denoted with an upward pointing arrow. It is labeled “z” in the first diagram. Arrows similarly identify the x-axis with an arrow pointing from the rear left to the right front, diagonally across the figure and the y-axis with an arrow pointing from the left front diagonally across the figure to the right rear of the diagram. These axes are similarly labeled as “x” and “y.” In this first diagram, four orange balloon-like shapes extend from a point at the origin out along the x- and y- axes in positive and negative directions covering just over half the length of the positive and negative x- and y- axes. Beneath the diagram is the label, “d subscript ( x superscript 2 minus y superscript 2 ).” The second diagram just right of the first is similar except the x, y, and z labels have been replaced in each instance with the letter L. Only a pair of the orange balloon-like shapes are present and extend from the origin above and below along the vertical axis. An orange toroidal or donut shape is positioned around the origin, oriented through the x- and y- axes. This shape extends out to about a third of the length of the positive and negative regions of the x- and y- axes. This diagram is labeled, “d subscript ( z superscript 2 ).” The third through fifth diagrams, similar to the first, show four orange balloon-like shapes. These diagrams differ however in the orientation of the shapes along the axes and the x-, y-, and z-axis labels have each been replaced with the letter L. Planes are added to the figures to help show the orientation differences with these diagrams. In the third diagram, a green plane is oriented vertically through the length of the x-axis and a blue plane is oriented horizontally through the length of the y-axis. The balloon shapes extend from the origin to the spaces between the positive z- and negative y- axes, positive z- and positive y- axes, negative z- and negative y- axes, and negative z- and positive y- axes. This diagram is labeled, “d subscript ( y z ).” In the fourth diagram, a green plane is oriented vertically through the x- and y- axes and a blue plane is oriented horizontally through the length of the x-axis. The balloon shapes extend from the origin to the spaces between the positive z- and negative x- axes, positive z- and positive x- axes, negative z- and negative x- axes, and negative z- and positive x- axes. This diagram is labeled “d subscript ( x z ).” In the fifth diagram, a pink plane is oriented vertically through the length of the y-axis and a green plane is oriented vertically through the length of the x-axis. The balloon shapes extend from the origin to the spaces between the positive x- and negative y- axes, positive x- and positive y- axes, negative x- and negative y- axes, and negative x- and positive y- axes. This diagram is labeled, “d subscript ( x y ).”
The directional characteristics of the five d orbitals are shown here. The shaded portions indicate the phase of the orbitals. The ligands (L) coordinate along the axes. For clarity, the ligands have been omitted from the d x 2 − y 2 orbital so that the axis labels could be shown.

In an uncomplexed metal ion in the gas phase, the electrons are distributed among the five d orbitals in accord with Hund's rule because the orbitals all have the same energy. However, when ligands coordinate to a metal ion, the energies of the d orbitals are no longer the same.

Questions & Answers

Three charges q_{1}=+3\mu C, q_{2}=+6\mu C and q_{3}=+8\mu C are located at (2,0)m (0,0)m and (0,3) coordinates respectively. Find the magnitude and direction acted upon q_{2} by the two other charges.Draw the correct graphical illustration of the problem above showing the direction of all forces.
Kate Reply
To solve this problem, we need to first find the net force acting on charge q_{2}. The magnitude of the force exerted by q_{1} on q_{2} is given by F=\frac{kq_{1}q_{2}}{r^{2}} where k is the Coulomb constant, q_{1} and q_{2} are the charges of the particles, and r is the distance between them.
Muhammed
What is the direction and net electric force on q_{1}= 5µC located at (0,4)r due to charges q_{2}=7mu located at (0,0)m and q_{3}=3\mu C located at (4,0)m?
Kate Reply
what is the change in momentum of a body?
Eunice Reply
what is a capacitor?
Raymond Reply
Capacitor is a separation of opposite charges using an insulator of very small dimension between them. Capacitor is used for allowing an AC (alternating current) to pass while a DC (direct current) is blocked.
Gautam
A motor travelling at 72km/m on sighting a stop sign applying the breaks such that under constant deaccelerate in the meters of 50 metres what is the magnitude of the accelerate
Maria Reply
please solve
Sharon
8m/s²
Aishat
What is Thermodynamics
Muordit
velocity can be 72 km/h in question. 72 km/h=20 m/s, v^2=2.a.x , 20^2=2.a.50, a=4 m/s^2.
Mehmet
A boat travels due east at a speed of 40meter per seconds across a river flowing due south at 30meter per seconds. what is the resultant speed of the boat
Saheed Reply
50 m/s due south east
Someone
which has a higher temperature, 1cup of boiling water or 1teapot of boiling water which can transfer more heat 1cup of boiling water or 1 teapot of boiling water explain your . answer
Ramon Reply
I believe temperature being an intensive property does not change for any amount of boiling water whereas heat being an extensive property changes with amount/size of the system.
Someone
Scratch that
Someone
temperature for any amount of water to boil at ntp is 100⁰C (it is a state function and and intensive property) and it depends both will give same amount of heat because the surface available for heat transfer is greater in case of the kettle as well as the heat stored in it but if you talk.....
Someone
about the amount of heat stored in the system then in that case since the mass of water in the kettle is greater so more energy is required to raise the temperature b/c more molecules of water are present in the kettle
Someone
definitely of physics
Haryormhidey Reply
how many start and codon
Esrael Reply
what is field
Felix Reply
physics, biology and chemistry this is my Field
ALIYU
field is a region of space under the influence of some physical properties
Collete
what is ogarnic chemistry
WISDOM Reply
determine the slope giving that 3y+ 2x-14=0
WISDOM
Another formula for Acceleration
Belty Reply
a=v/t. a=f/m a
IHUMA
innocent
Adah
pratica A on solution of hydro chloric acid,B is a solution containing 0.5000 mole ofsodium chlorid per dm³,put A in the burret and titrate 20.00 or 25.00cm³ portion of B using melting orange as the indicator. record the deside of your burret tabulate the burret reading and calculate the average volume of acid used?
Nassze Reply
how do lnternal energy measures
Esrael
Two bodies attract each other electrically. Do they both have to be charged? Answer the same question if the bodies repel one another.
JALLAH Reply
No. According to Isac Newtons law. this two bodies maybe you and the wall beside you. Attracting depends on the mass och each body and distance between them.
Dlovan
Are you really asking if two bodies have to be charged to be influenced by Coulombs Law?
Robert
like charges repel while unlike charges atttact
Raymond
What is specific heat capacity
Destiny Reply
Specific heat capacity is a measure of the amount of energy required to raise the temperature of a substance by one degree Celsius (or Kelvin). It is measured in Joules per kilogram per degree Celsius (J/kg°C).
AI-Robot
specific heat capacity is the amount of energy needed to raise the temperature of a substance by one degree Celsius or kelvin
ROKEEB
Got questions? Join the online conversation and get instant answers!
Jobilize.com Reply
<< Chapter < Page Page > Chapter >>
Practice Key Terms 11

Read also:

Get Jobilize Job Search Mobile App in your pocket Now!

Get it on Google Play Download on the App Store Now




Source:  OpenStax, Chemistry. OpenStax CNX. May 20, 2015 Download for free at http://legacy.cnx.org/content/col11760/1.9
Google Play and the Google Play logo are trademarks of Google Inc.

Notification Switch

Would you like to follow the 'Chemistry' conversation and receive update notifications?

Ask