COLOR OF TRANSITION METAL COMPLEXES

The human eye perceives a mixture of all the colors, in the proportions
present in sunlight, as white light. Complementary colors, those located
across from each other on a color wheel, are also used in color vision.
For example, when red photons are absorbed from white light, the eyes
see the color green. When violet photons are removed from white light,
the eyes see lemon yellow.

The blue color of the [Cu(NH3)4]2+ ion results because this ion absorbs
orange and red light, leaving the complementary colors of blue and
green. If white light (ordinary sunlight, for example) passes through
[Cu(NH3)4]SO4 solution, some wavelengths in the light are absorbed by
the solution. The [Cu(NH3)4]2+ ions in solution absorb light in the red
region of the spectrum. The light which passes through the solution and
out the other side will have all the colors in it except for the red. We
see this mixture of wavelengths as pale blue (cyan).
The striking colors exhibited by transition-metal complexes are caused
by excitation of an electron from a lower-energy d orbital to a higher-
energy d orbital, which is called a d–d transition.

The octahedral complex [Ti(H2O)6]3+ has a single d electron. To excite this

electron from the ground state t2g orbital to the eg orbital, this complex
absorbs light from 450 to 600 nm. The maximum absorbance corresponds
to Δo and occurs at 499 nm. Calculate the value of Δo in Joules and predict
what color the solution will appear.

Solution
We can convert wavelength to frequency:

ν= c/λ =3.00×108m/s(499nm)×(1m/109nm)
=6.01×1014s−1=6.01×1014Hz

And then using Planck's equation that related the frequency of light to
energy

E=hν

so

E=(6.63×10−34J-s) × (6.01×1014Hz
=3.99×10−19J

Because the complex absorbs 600 nm (orange) through 450

(blue), the indigo, violet, and red wavelengths will be transmitted, and
the complex will appear purple.

Color Depends on Ligand Field

The specific ligands coordinated to the metal center also influence the color
of coordination complexes. Because the energy of a photon of light is
inversely proportional to its wavelength, the color of a complex depends on
the magnitude of Δo, which depends on the structure of the complex. For
example, the complex [Cr(NH3)6]3+ has strong-field ligands and a relatively
large Δo. Consequently, it absorbs relatively high-energy photons,
corresponding to blue-violet light, which gives it a yellow color. A related
complex with weak-field ligands, the [Cr(H2O)6]3+ ion, absorbs lower-
energy photons corresponding to the yellow-green portion of the visible
spectrum, giving it a deep violet color. For example, the iron (II) complex
[Fe(H2O)6]SO4 appears blue-green because the high-spin complex absorbs
photons in the red wavelengths. In contrast, the low-spin iron(II) complex
K4[Fe(CN)6] appears pale yellow because it absorbs higher-energy violet
photons.
In general, strong-field ligands cause a large split in the energies of d
orbitals of the central metal atom (large Δoct). Transition metal
coordination compounds with these ligands are yellow, orange, or red
because they absorb higher-energy violet or blue light. On the other hand,
coordination compounds of transition metals with weak-field
ligands are often blue-green, blue, or indigo because they absorb
lower-energy yellow, orange, or red light.

Strong-field ligands cause a large split in the energies of d orbitals

of the central metal atom and transition metal coordination
compounds with these ligands are typically yellow, orange, or red
because they absorb higher-energy violet or blue light.
Coordination compounds of transition metals with weak-field
ligands are often blue-green, blue, or indigo because they absorb
lower-energy yellow, orange, or red light.

Identify the color (either blue, green, yellow, or orange) for the following
complex ions formed with Co3+:

a. [Co(CN)6]3-
b. [Co(NH3)6]3+
c. [CoF6]−4
d. [Co(H2O)6]3+

Solution

Each of these complex ions has the same metal with the same oxidation
state, so the ligand field is the relevant factors. Each of the complex ions
also has an octahedral ligand field, so we only need to compare the
strength of the ligands in determining Δo, which is determined by the
spectrochemical series.

The ligands for each complex ions are: (a) CN−, (b) NH3 (c) F− and
(d) H2O which are ranked in increasing Δo magnitude:
 F− < H2O < NH3 <CN−

The relationship between the ΔoΔo and the energy of the photons are
absorbed in the d-d transition of Co3+Co3+ is given by equating Planck's
equation to the crystal field splitting parameter:

E=hν =hc/λ =Δo

Now, we need to get a relative correlation between observed color (to the
eye) and the wavelength of the light that is absorbed. From the
complementary color wheel in Fi we get the following relationships
(arranged from highest energy absorbed to lowest):

• 400-nm Violet light absorbed → Green-yellow observed

• 430-nm Blue light absorbed → Orange observed
• 450-nm Blue light absorbed → Yellow observed
• 490-nm Blue-green light absorbed → Red observed
• 570-nm Yellow-green light absorbed → Violet observed
• 580-nm Yellow light absorbed → Dark blue observed
• 600-nm Orange light absorbed → Blue observed
• 650-nm Red light absorbed → Green observed

Of the four possible colors given in the problem (blue, green, yellow, and
orange), the corresponding colors that are absorbed are (600 nm, 650 nm,
450 nm, and 430, respectively). From Equation the smaller λ of absorbed
light corresponds to the higher energy photons, so we would correlate the
four wavelengths of absorbing photons in terms of increasing energy to
observed color:

650nmgreen<600nmblue<450nmyellow<430nmorange

Now, just correlate the ranking in Equation to the ranking

in Equation
F−⏟green<H2O⏟blue<NH3⏟yellow<CN−⏟orange

and more specifically in terms of the original question

[CoF6]−3green<[Co(H2O)6]3+blue<[Co(NH3)6]3+yellow<[Co(CN)6]−3o
range

Magnetic Properties of Transition Elements

Most of the transition elements show paramagnetic behavior. The unpaired
electrons in (n-1) d orbitals are responsible for the magnetic properties. The
paramagnetic character of the transition metals increases on moving from left to
right as the number of unpaired electrons increases from one to five. The middle
elements are found to possess the maximum paramagnetic property. The
magnetic properties decrease with the decrease in the number of unpaired
electrons. The transition metals which contain paired electrons depict
diamagnetic behavior.

Explanation for magnetic properties

An electron is a charged particle (negatively charged) which revolves
around the nucleus and spins on its own axis. A magnetic field is
generated due to the orbital motion and spin of the electron. The
spinning of an electron in an orbit is very much similar to the flow of
electric current in a closed circuit. Therefore, an unpaired electron is
regarded as a micro magnet which has a definite magnetic moment. A
substance which contains an unpaired electron when placed in a
magnetic field interacts with the applied field. Consequently, an
attractive force is exerted and the paramagnetic property is shown. The
number of unpaired electrons determines the magnitude of the
magnetic moment. The higher the number of unpaired electrons, the
more the magnetic moment and the greater will be the paramagnetic
behaviour of the substance.

In the case of paired electrons, the electrons in each pair will have an
opposite spin. The magnetic field created by the electrons of the same
pair is equal and opposite in nature. Hence, the magnetic field which is
created by one electron is cancelled by the other. So the net effect of
the magnetic moment is zero. These kinds of substances show
diamagnetic properties and are repelled by the applied magnetic field.

Oxidation states
Oxidation states are numbers assigned to ions that show how many electrons the
ion has lost or gained, compared to the element in its uncombined state. A
positive oxidation state shows that the element lost electrons, whilst a negative
oxidation state shows that it gained electrons. They can also be referred to as
oxidation numbers.

Question
1. Why do transition elements show variable oxidation states?
2. Name the element showing the maximum number of oxidation states
among the first series of transition metals from Sc(Z=21) to Zn(Z=30).
3. Name the element which shows only +3 oxidation state.

Solution
Variable oxidation states in transition elements
 • Transition elements show variable oxidation states because their
valence electrons are in two different sets of orbitals, i.e. in (n-
1)d and ns orbitals.
• The energy difference between these orbitals is very less, hence
both the energy levels can be used for bond formation.
• Hence, this results in transition elements having variable
oxidation states.
Element in the first transition series with the maximum number of
oxidation states
• Manganese, i.e. Mn(Z=25), has an electronic
configuration [Ar]3d54s2.
• It has the highest number of unpaired electrons in the d-subshell.
• Since both d and s orbitals are used for bond formation,
total 5+2=7electrons are available for bond formation.
• Hence, Mn shows the highest oxidation state of +7 among the first series of
transition metals.
Element which shows only +3 oxidation state
• Scandium (Sc)exhibits +3 oxidation state in these series.
• The electronic configuration of Scandium (Sc) is [Ar] 3d¹ 4s².
• Since both d and s orbitals are used for bond formation, total 1+2=3
electrons are available for bond formation.
• Hence (Sc)exhibits +3 oxidation state.