<< Chapter < Page 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

hydrogen is a monovalent why aluminum is a divalent
Naldo Reply
Did you mean trivalent? This is because Aluminium has three electroms orbiting in the valence (furthest shell) which are involved in covalent bonding where each electron becomes a pair with another one in the other non metal and make a single bond. N. B: each single covalent bond contains 2 electr
Abdelkarim
Electrons, one from each atom. Did you know that god said '' And, [O Muhammad], you are not [engaged] in any matter or recite any of the Qur'an and you [people] do not do any deed except that We are witness over you when you are involved in it. And not absent from your Lord is any [part] of an atom
Abdelkarim
... atom's weight within the earth or within the heaven or [anything] smaller than that or greater but that it is in a clear register. ''
Abdelkarim
wat gives perfume it's sweet smell
Olaobaju Reply
These are organic compounds, which have plentiful functional groups which react with certain substances through a pathway in the cells lining nostrils which sends impulses that make you sense its sweet. Did you prophet Muhammad (peace upon him) encourages the use of perfume.
Abdelkarim
what is it use for
amagai
Prophet Muhammad (peace be upon him) used to love cleanliness and good scent. ... It was highlighted, in many hadiths, his love for fragrance and good scent like musk, 'ud and ambergris.
Abdelkarim
the types of giant covalent structure
Nobert Reply
define the following terms. electrovalent bonding
Nobert
 An unknown noble gas was allowed to flow into a 300.0 mL glass bulb until the P = 685 torr. Initially, the glass bulb weighed 32.50 g, but now it weighs 33.94 g. If the temperature is 27.0 °C, what’s the identity of the gas?
Roseline Reply
* Use PV=nRT with correct units to find n (number of moles) * Use n = mass/ Ar (Ar is relative atomic mass) Ar = 131.15 -> Xenon N. B: P is in pascals, V in m3, n in mol, R in J/ k. Mol, T in kelvin *Thank God
Abdelkarim
N. B: As it is a noble gas it is mono-atomic so the Ar does not need to be divided by two (not diatomic).
Abdelkarim
what is molecule
Olom Reply
molecules are produced by double atom from example this is hydrogen atom and this is hydrogen2 are call that hydrogen molecules or gass
Naldo
What is the generic name for the compound
Orisanmi Reply
what is the formular for methane
Tamaranimiweremi Reply
CH4 , it is the simplest alkane
Abdelkarim
what is the formula for alkaline
Olom
hi
Yusuf
I wish to learn to more of chemistry, can someone please teach me.
Yusuf
what is zero gravity
Blessing Reply
every object is that zero gravity
Rabiu
Probably when an object is in space and there are no nearby masses that pull her, and exert gravity
Abdelkarim
Alright. .good job
Rabiu
And all majesty to God, (وَهُوَ ٱلَّذِی خَلَقَ ٱلَّیۡلَ وَٱلنَّهَارَ وَٱلشَّمۡسَ وَٱلۡقَمَرَۖ كُلࣱّ فِی فَلَكࣲ یَسۡبَحُونَ) [سورة الأنبياء 33 And it is He who created the night and the day and the sun and the moon; all [heavenly bodies] in an orbit are swimming. General theory of relativity in Qur
Abdelkarim
what is molecule?
Olom
what is lattice energy
Getrude Reply
why is CO a neutral oxide and CO2 an acidic oxide
Emmanuel Reply
Because when CO2 dissolves in water forming a weak acid. CO does not dissolve in water as it has strong triple bond.
Abdelkarim
What is acid
Progress Reply
which donate H+ or accept lone pair of electron
Kajal
kinetic theory of matter and gas law
Victoria Reply
hi
Victoria
pls explain
Victoria
what is clay
Thankgod Reply
material containing clay minerals. Clays develop plasticity when wet, due to a molecular film of water surrounding the clay particles, but become hard, brittle and non–plastic upon drying or firing. Most pure clay minerals are white or light-coloured, but natural clays show a variety of colours
Abdelkarim
due iron oxide. The four types of clay are Earthenware clay, Stoneware clay, Ball clay, and Porcelain. All of them can be used to make pottery, but the end result would differ a lot thanks to their different textures, colors, and flexibilities.
Abdelkarim
And do you know that god has created human from clay (وَلَقَدۡ خَلَقۡنَا ٱلۡإِنسَـٰنَ مِن صَلۡصَـٰلࣲ مِّنۡ حَمَإࣲ مَّسۡنُونࣲ) [سورة الحجر 26] And We did certainly create man out of clay from an altered black mud. You can install Quran from paly store for free with translations.
Abdelkarim
darw a periodic table
Hazard Reply
draw a periodic table
Hazard
You will arrange the elements into row and coloumns according to increasing proton number. You may want to use symbols or their names. Hydrogen, Helium, etc. God has created all these elements from nothing, in Islam we know God is the creator.
Abdelkarim
why are you drawing a periodic table? why not just print one from the internet and use as a reference
Jakhari
Great thought
Bright
how are you?
Abel Reply
alright , how about you
Marina
am fine
Agbo
your name is Agbo?
Marina
my name is amel
Farid
l use the email of my husband
Farid

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