Transition Metal Chemistry

The elements of the fourth period of the Periodic Table are referred to as the First Transition
Series or First Row of Transition Metals. These elements are:

Sc Ti V Cr Mn Fe Co Ni Cu Zn

They are all metals with remarkably similar chemical and physical properties.

A transition element can be defined as a d-block element which forms some compounds in which
there is a partly-filled ‘d’ subshell of electrons. According to this definition, Sc3+ (3d0) and Zn2+
(3d10) are not considered as transition metal ions.

As you move across this Period from left to right, each successive element has an additional
proton and one additional electron. Each added electron however, is added to the 3d subshell
(i.e. the penultimate subshell). As a result, the 4s (valence) electrons experience an almost
consistent level/ amount of shielding across the Period. Therefore, first row transition metals
are very similar in both size and ionization energies.

➢ Electronic configuration of Transition Metals

▪ Aufbau Principle

Energy of a 3d subshell > Energy of a 4s subshell

This means therefore, that the 4s subshell will be filled before the 3d.

▪ Hunds’ Rule of Maximum Multiplicity

After the 4s electrons have been filled in, the 3d subshell is the next to be occupied. Remember
that there are 5 degenerate orbitals in the 3d subshell: dxy, dyz, dxz, dx2-y2, dz2. Each subshell
will be occupied singly first and then spin-pairing of electrons will occur.

A general transition metal may be represented as:

[Ar] 3dx 4sy where: [Ar] = 1s22s22p63s23p6

x has values from 1-10; y has values of 1 or 2

Therefore:

Ca - [Ar] 3d0 4s2 (a p-block element)

Sc - [Ar] 3d1 4s2 (a transition metal or d-block element)

The electronic configuration for all 10 transition metal elements:

Exceptions:

Transition elements are therefore defined as elements where atoms have partially filled d-orbitals
or which form compounds in which their ion has an incomplete subshell of 3d electrons.

By this definition, the transition metal ions: Sc3+, Cu+ and Zn2+ do not meet the definition of a
transition metal ion but they are included nonetheless.
Cr and Cu are two anomalies in the electronic configuration of the 1st row transition series:

Expected Actual

Cr 3d44s2 3d54s1

Cu 3d94s2 3d104s1

This occurs because a half-filled d-orbital (for Cr) and a full d-orbital (for Cu) are very stable
arrangements of electrons. Hence, one of the two 4s electrons is transferred to a 3d subshell to
create the stable half-filled or filled 3d configuration.

➢ Forming transition metal ions

When electrons are being filled (into 3d and 4s subshells), the 4s is filled first because it is of
lower energy than the 3d. However, when electrons are being lost (to form ions), it is the 4s
electrons that are lost first, then the 3d electrons.

This may appear to be contrary since one would expect the electrons in the higher-energy 3d
orbital to be lost first. This assumes however that the orbitals maintain their same relative
energies in the empty state as when they are filled.

This is INCORRECT.

Consider Ca and Sc:

____

4s ____

____ ____ 3d

4s 3d Ca Sc

Filling a 3d subshell (with at least one electron) causes the 4s orbital to exist at a higher
energy.

This occurs because the 3d orbitals are lobe-shaped and can move closer to the nucleus of the
atom than the 4s orbital, which has a spherical shape. Hence, when an electron enters the 3d
orbital, it will effectively screen the 4s electrons thereby raising their energy and making them
the first to be lost.
Chemical properties of transition metal elements:

▪ They have variable oxidation states.

▪ They can act as homogenous and heterogeneous catalysts.
▪ They have important magnetic properties e.g. paramagnetism.
▪ They form complex ions.
▪ They form colored complexes/ compounds.

➢ Variable oxidation states

Most of the transition elements can form compounds in which their oxidation state differs from
one compound to the next.

Moving across the 1st Row transition series, the maximum oxidation state increases from +3
(Sc) to +7 (Mn) then decreases again to +2 (Zn), with the most common oxidation state
being +2.

This occurs because moving across the Period, there comes a point (i.e. after Mn) where the
increasing nuclear charge of each successive atom enables the 3d electrons to become even more
strongly attracted to the nucleus and therefore less likely to be lost in order to form ions (Recall:
when going across a Period, the number of protons increases.). Also, electron pairing in the
atoms of the elements after Mn makes the loss of 3d electrons more difficult since it requires
more energy to remove an electron from a spin-pair than to remove a single electron.

N.B.: You do not have to learn this table

 ➢ Catalysis

Transition metals, both in their elemental form and in their compounds, are effective and
important catalysts. Remember that a catalyst is a substance that alters the rate of a reaction
without itself undergoing any permanent chemical change. They achieve this by offering an
alternative pathway for the reaction, which involves a lower activation energy.

Transition metals and their complexes/ compounds may act as either homogeneous or
heterogeneous catalysts.

Heterogeneous catalyst – the catalyst is in a different physical state from the reactants

e.g. a finely divided solid catalyst in the presence of liquid or gaseous reactants

The behaviour/ action of heterogeneous catalysts is explained by the Adsorption Theory.

Adsorption refers to the adherence of molecules on the surface of a substance. Note that this is
different from absorption, which involves the intake of molecules into the interior of a substance.

For heterogeneous catalysis to occur, the reactant molecules need to be readily adsorbed unto the
catalyst’s surface. With transition metals, this is achieved through the availability of
partially-filled d-orbitals, which allow bonding with the reactants.

e.g. Consider the hydrogenation of ethene (gas) by hydrogen (gas) to yield ethane (gas) in the
presence of finely-divided nickel catalyst (solid):

C2H4 (g) + H2 (g) C2H6 (g)

The ethene and hydrogen gas molecules first adsorb unto the surface of the solid nickel catalyst.

In this way, the reactant molecules are brought closer together and successful collisions can
occur between them in order to produce the product, in this case ethane gas.

The product formed is then released from the surface of the nickel and the entire process is
repeated with other reactant molecules to form more product.
Homogeneous catalysts - the catalyst is in the same physical state as the reactants, most
commonly in solution form.

This catalytic process usually proceeds via the formation of some intermediate complex.

The ability of transition metals to form ions of varying oxidation states is an important
factor in their ability to act as homogeneous catalysts.

e.g. Consider the following uncatalyzed reaction:

S2O82- (aq) + 2I- (aq) 2SO42- (aq) + I2 (aq)

The above reaction may be catalyzed by Fe2+ (aq) ions:

S2O82- (aq) + 2Fe2+ (aq) 2SO42- (aq) + 2Fe3+ (aq)

2I- (aq) + 2Fe3+ (aq) I2 (aq) + 2Fe2+ (aq)

The intermediate (Fe3+ (aq)) reflects a change in oxidation state of iron from +2 to +3, then back
to +2 (Recall: catalysts must remain unchanged at the end of a reaction).

➢ Complexes

Metal complexes (or simply complexes) are comprised of a central metal ion bonded to a group
of surrounding molecules or ions.

If the complex carries a net charge, it is called a complex ion e.g. [Ag(NH3)2]+

Compounds that contain complexes are known as coordination compounds.

Many coordination compounds contain transition metal ions, although ions of other metals can
also form complexes.

The molecules or ions that bond to the metal ions in a complex are known as ligands. e.g. there
are 2 ligands bonded to the Ag+ ion in [Ag(NH3)2]+.

Each ligand functions as a Lewis base by donating a pair of electrons to the metal to form a
bond.
Therefore, every ligand has at least one lone pair of electrons in their outer shell. e.g. H2O,
NH3, Cl-, CN-

As such, most ligands are either polar molecules or anions. That is, a ligand can either be a
neutral molecule or have a formal negative charge.

In forming a complex, the ligands are said to coordinate to the metal.

Coordination number – the no. of atoms directly bonded to the central metal ion in a complex

The central metal and the ligands bound to it constitute the coordination sphere of the complex.

Donor atom – the atom of the ligand that is bound directly to the metal e.g. N is the donor atom
in [Ag(NH3)2]+

e.g. Ligand Donor Atom

NH3 N

H2O O

Cl- Cl

There are different ways to arrange ligands around the metal ion in complexes. This gives rise to
the formation of isomers, different shapes of complexes, as well as different colors of complexes.

Some metals exhibit constant coordination numbers e.g. for Cr(III) and Co(III) ions, the
coordination number is 6; for Pt(III) ions, the coordination number is 4.

The most common coordination numbers are 4 and 6.

The coordination number of a metal ion is often influence by the relative size of the metal ion
and the surrounding ligands. As the ligand gets larger, fewer ligands can coordinate to the metal
ion. e.g. iron(III) is able to coordinate to 6 fluorides in [FeF6]3- but to only 4 chlorides in [FeCl4]-.

4-coordinate complexes have two common geometries: tetrahedral and square planar. The
tetrahedral geometry is the more common of the two.

The vast majority of 6-coordinate complexes have an octahedral geometry.

 ➢ The metal-ligand bond

The bond between a ligand and a metal ion is an example of an interaction between a Lewis acid
and a Lewis base. Ligands are Lewis bases due to the presence of their lone pair of electrons.
Metal ions (particularly transition metal ions) are Lewis acids as they have empty d-orbitals in
their valence/ outer shell to accept electrons.

The formation of metal-ligand bonds can markedly alter the properties observed for a metal ion.
A metal complex is a distinct chemical species that has physical and chemical properties
different from the metal ion and the ligands that formed it. Complexes for example, may have
colors that differ dramatically from those of their component metal ions or ligands.

e.g. Fe3+ (aq) is a yellow solution but [Fe(H2O)5SCN]2+ (aq) is a bright red solution.

Hydrated metal ions are actually complex ions in which the ligand is water e.g. Fe3+ (aq) is really
[Fe(H2O)6]3+ (aq).

Other complexes are able to form in aqueous solutions because ligands like NH3, CN- and
SCN- can replace these coordinated H2O molecules/ ligands in the hydrated complexes.

Because of their small size and vacant d-orbitals, transition metals often exist as aqua-
complexes (i.e. in their hydrated form) in aqueous solution instead of the free ions.

e.g. Co2+ is usually bonded to 6 water molecules:

In the above e.g., the lone pair of electrons on the O atom of a water molecule is donated to the
central metal ion. This bond formation results in a dative or coordinate covalent bond being
formed (where 1 species provides both bonding electrons). This is usually assumed to be the
case for all transition metal complexes.

In transition metal complexes, the transition metal ion is the central metal ion since it is
accepting the electron pairs; it is acting as the Lewis acid.
Conversely, the chemical species that is donating the pair of electrons is the ligand, where it is
acting as the Lewis base.

Ligands are often characterized according to the number of different bonds that they can
form with the central metal ion.

Monodentate ligand – only 1 pair of electrons is donated therefore, only 1 bond is formed

Monodentate ligands possess a single donor atom and are able to occupy only 1 site in a
coordination sphere. eg. H2O, Cl-

Chelating ligands

These are so called because they form ring-like structures when coordinated to the central metal
ion. Two or more donor atoms occupy two or more coordination sites in the coordination sphere.

Bidentate ligands – these form 2 bonds per ligand with the central metal ion e.g.
ethylenediamine, abbreviated ‘en’. e.g. [Ni(en)3]2+ and oxalate (C2O42-) e.g. [Ni(C2O4)3]4-

or ethylenediamine (‘en’)

bipyridine oxalate (C2O42-)

e.g. (i) e.g. (ii)

Both N atoms of ‘en’ each have a lone pair of electrons to donate in [Ni(en)3]2+ (e.g. (i)).

Two O atoms of oxalate each have a lone pair of electrons to donate in [Ni(C2O4)3]4- (e.g. (ii)).

Polydentate ligands – capable of forming multiple bonds with the central metal ion e.g. EDTA
(ethylenediaminetetraacetic acid) is an important polydentate ligand having 6 donor atoms.

In general, chelating ligands or chelating agents form more stable complexes than do
monodentate ligands.

EDTA

Chelating agents are of great importance as they are used to remove metal ions from
reactions or systems. They are used in medicine to remove metal ions such as Hg2+, Pb2+ and
Cd2+ which are detrimental to health. e.g. One method of treating lead poisoning is to administer
EDTA. The EDTA chelates the lead, allowing it to be removed from the body via urine.
Chelating agents are also quite common in nature. Mosses and lichens secrete chelating agents to
capture metal ions from the rocks they inhabit.

Depending on the pH, the number of bonds EDTA may form with the metal ion varies:

▪ Acidic conditions:

Under acidic conditions, the –COOH groups will have a tendency to remain protonated and
hence not coordinate significantly via the O atoms, therefore only the 2 N atoms will act as
donor atoms. The EDTA molecule is the ligand.

▪ Basic conditions:

In base, the –COOH groups will be ionized to yield –COO- and these negatively-charged
anions may now act as donor atoms as well. Thus, the EDTA4- anion is now the ligand.

EDTA4-

(Unless otherwise indicated, EDTA usually bonds to a metal ion as the EDTA4- anion.)
e.g.
N.B.: These are just examples; you will not be asked to draw EDTA complexes

➢ Depiction of transition metal complexes

Transition metal complexes are represented by square brackets [ ] enclosing the central metal
ion and its ligands (i.e. the coordination sphere). Spectator ions are those that are not directly
coordinated to the central metal ion but are required to maintain charge neutrality (i.e. form a
neutral compound) and are represented on the outside of the brackets (i.e. they are outside of the
coordination sphere).

This distinction is important when considering the chemical reactions of transition metal
isomers:

e.g. Consider the following 3 compounds:

(a) [Co(NH3)6]Cl3

(b) [Co(NH3)3Cl3]

(c) [Co(NH3)5Cl]Cl2

In ALL of the above cases, NH3 ligands are present and Cl may act as either a ligand or a
spectator ion. The Co ion is in the +3 oxidation state.
What would be observed if AgNO3 (aq) were added to separate solutions of (a), (b) and (c)?

(a) [Co(NH3)6]Cl3 [Co(NH3)6]3+ (aq) + 3Cl- (aq)

Then: 3Cl- (aq) + 3Ag+ (aq) 3AgCl (s) (i.e. a ppt. formed)

(b) [Co(NH3)3Cl3] no visible rxn. with AgNO3 (aq) (i.e. no ppt. formed)

(c) [Co(NH3)5Cl]Cl2 [Co(NH3)5Cl]2+ (aq) + 2Cl- (aq)

Then: 2Cl- (aq) + 2Ag+ (aq) 2AgCl (s) (ppt. formed)

➢ Determination of charge

The charge on a transition metal complex is the sum of the charges on the central metal ion and
the ligands:

Total Charge on complex = Charge on metal ion + Charge on all ligands

Determining the formula of a complex ion

e.g. (1) A complex ion contains a chromium(III) ion bound to four water molecules and two
chloride ions. What is its formula?

Water is a neutral ligand; a chloride ion has a charge of -1.

Total Charge on complex ion = Charge on metal ion + Charge on all ligands

= (+3) + 4(0) + 2(-1)

= +1

The formula of the complex ion is therefore [Cr(H2O)4Cl2]+.

e.g. (2) What is the formula of the complex formed by a Pt(II) ion surrounded by two ammonia
molecules and two bromide ions?

[Pt(NH3)2Br2]
Determination of charge on the central metal ion

e.g. (1) Consider the complex: [Cu(NH3)4]2+

What is the charge on Cu?

NH3 are neutral ligands.

Total Charge on complex ion = Charge on metal ion + Charge on all ligands

+2 = Charge on Cu ion + 4(0)

+2 = Charge on Cu ion

Therefore, the charge on Cu in this complex is +2.

e.g. (2) What is the oxidation state of Rh in the compound [Rh(NH3)5Cl](NO3)2 ?

[Rh(NH3)5Cl](NO3)2 [Rh(NH3)5Cl]2+ + 2NO3-

Considering: [Rh(NH3)5Cl]2+ :

Charge on NH3 = 0; charge on Cl = -1.

Total Charge on complex ion = Charge on metal ion + Charge on all ligands

+2 = Charge on Rh ion + 5(0) + 1(-1)

+2 = Charge on Rh ion – 1

+3 = Charge on Rh ion

Therefore, the oxidation state of Rh in this complex is +3.

 ➢ Nomenclature (Naming) of transition metal complexes

Several rules should be followed when naming transition metal complexes:

1. In a compound, the cation is always named before the anion (regardless of whether it
is a complex ion or a spectator ion).

e.g. [Cu(H2O)6]Cl2 = [Cu(H2O)6]2+ + 2Cl-

named first

2. In the complex itself, the ligands are named before the transition metal.

i) The number of the particular type of ligand is indicated by its prefix:

e.g. 2 ligands – di 4 ligands – tetra 6 ligands – hexa

3 ligands – tri 5 ligands – penta

If the ligand itself contains a prefix of this kind (e.g. ethylenediamine), the alternative prefixes:
bis- and tris- are used and the ligand name is placed in brackets.

e.g. [Co(en)3]Br3 – tris(ethylenediamine)-cobalt(III) bromide

ii) Where there is >1 type of ligand present in the complex, they are named in alphabetical
order, ignoring their prefix.

e.g. [Co(NH3)5Cl]2+

There are: 5 NH3 ligands – prefix: penta

1 Cl ligand – prefix: no prefix

Ammonia will be named before the chloride ligand.

3. The oxidation state of the transition metal ion is placed in brackets as Roman
numerals after the name or symbol of the metal.
 4. Depending on whether the species is a ligand or spectator ion, negatively charged or
neutral, certain rules apply in its nomenclature:

i) Negatively charged species:

If it is a spectator ion, it keeps its usual name.

If it is a ligand, its name ends in “o” instead of “ide”.

e.g. As a spectator ion As a ligand

Cl- chloride chloro

CN- cyanide cyano

OH- hydroxide hydroxo

ii) Neutral molecules:

As a ligand, it will maintain its normal name, with certain important exceptions:

H2O – aqua

NH3 – ammine

CO – carbonyl

e.g. Consider the following:

[Cu(H2O)6]Cl2 – hexaaquacopper(II) chloride

[Co(NH3)5Cl]Cl2 – pentamminechlorocobalt(III) chloride

iii) If the complex is negatively charged, “ate” is added to the end of the metal name.

e.g. [CoCl4]2- – tetrachlorocobaltate(II)

Certain metals however, tend to use their original Latin names in negatively charged complexes.

e.g. Fe – ferrate Cu – cuprate Ag – argentate

e.g. (1) Name the following compounds:

(a) [Fe(H2O)6]Cl2 – hexaaquairon(II) chloride

(b) Cr(OH)3(H2O)3 – triaquatrihydroxochromium(III)

(c) K2[CoCl4] – potassium tetrachlorocobaltate(II)

(d) [Cu(NH3)4(H2O)2](NO3)2 – tetraamminediaquacopper(II) nitrate

(e) K4[Fe(CN)6] – potassium hexacyanoferrate(II)

e.g. (2) Write the formula for the compound: pentamminechlorocobalt(II) chloride.

[Co(NH3)5Cl]Cl

➢ Shapes of complexes

i) Linear: coordination number = 2

Not common, except among certain copper(I) complexes

e.g. [Cu(NH3)2]+ =

ii) Octahedral: coordination number = 6

The most common geometry for aqua complexes of M2+ and M3+ ions, except [Zn(H2O)4]2+

Many ammine complexes and mixed ammine and aqua complexes also have octahedral
geometry.

e.g. [Cu(H2O)6]2+

[Cu(NH3)4(H2O)2]2+
 iii) For coordination number = 4, there are 2 possible geometries:

a) Tetrahedral

Most common among Zn(II) complexes e.g. [Zn(H2O)4]2+

All 4-coordinate halo complexes have tetrahedral geometry.

e.g. [CoCl4]2-

b) Square planar

Among the 1st Row transition metal elements, only certain nickel complexes adopt this
geometry.

e.g. [Ni(CN)4]2-
 Octahedral
and
Tetrahedral
complexes

y
 ➢ Transition metal isomerism

Recall: Isomers of a compound have the same molecular/ chemical formula but exist in different
structural forms i.e. have different arrangements of atoms.

Two of the most common type of isomerism presented by transition metal complexes are:

▪ Coordination Sphere Isomerism (a type of structural isomerism)

These isomers differ in whether an ion or molecule is directly bonded to the central metal ion
(i.e. acting as a ligand) or is outside of the coordination sphere (i.e. acting as a spectator ion).

e.g. [Co(NH3)4(OH)2]Cl2 vs. [Co(NH3)4Cl2](OH)2

with AgNO3 with AgNO3

2 mol AgCl (s) produced no visible reaction

Coordination sphere isomers differ in both their physical and chemical properties, such as
color and solubility.

e.g. CrCl3(H2O)6 has 2 coordination sphere isomers:

[Cr(H2O)6]Cl3 – a violet compound & [Cr(H2O)5Cl]Cl2 – a green compound

▪ Geometrical isomers (a type of stereoisomerism)

These complexes differ in their point of attachment of the ligands to the central metal ion.

These isomers usually occur in square planar and octahedral complexes but NOT tetrahedral
complexes.

Consider the square planar complexes of Pt(NH3)2Cl2:

Cis-platin

&

Trans-platin
Cis Trans

(same side) (opposite sides)

 The octahedral
complex:
[Co(NH3)4Cl2]+

Cis Trans

Geometric isomers have different properties as well e.g. colors, solubilities, melting and boiling
points. They can also have markedly different chemical reactivities. In the above example, cis-
platin is used as a drug in the treatment of cancer, while trans-platin is physiologically inactive.

➢ Acid-Base behaviour of transition metal ions

Ions of d-block elements tend to have a small size. When a high charge is present, these ions tend
to cause hydrolysis of water, producing H+ ions in solution.

e.g.

The consequence of this is that generally, ions with charge > +2 tend to from acidic solutions.

Therefore, M3+ (aq) ions tend to be appreciably more acidic than M2+ (aq) ions. This presents a
useful way for distinguishing between 2 such solutions.

e.g. How would one distinguish between solutions of Fe2+ (aq) and Fe3+ (aq)?

React both solutions with Na2CO3 (s):

Fe2+ (aq) + Na2CO3 (s) no reaction

H+
3+
Fe (aq) + Na2CO3 (s) Fe3+ (aq) + 2Na+ (aq) + CO2 (g) + H2O (l)

Effervescence (due to evolution of CO2 (g)) will be observed with the latter solution.
This is because Fe3+ (aq) solutions are more acidic than Fe2+ (aq) solutions and therefore will
react with Na2CO3.

▪ Oxycations

Ions with charge > +3 tend to permanently bond with oxygen of water to form oxycations.

exists as
4+
e.g. V VO2+ (vanadyl cation)
exist as
Ti4+ TiO2+ (titanyl cation)

i.e. V4+ and Ti4+ ions cannot be isolated, they have a great hydrolyzing power (they easily
hydrolyse water molecules to form oxycations).

▪ Oxyanions

Ions with even greater charge and smaller size will have a very high charge density ratio. This
enables them to hydrolyse an even greater number of water molecules and therefore bond to
more oxygen (O2-) species, forming oxyanions.

exists as
e.g. Mn7+ MnO4- (permanganate anion)
exists as
Cr6+ CrO42- (chromate anion)

Mn7+ and Cr6+ have a great hydrolyzing power.

➢ Significance of complexes in qualitative ion analysis

e.g. Tests for Fe2+ and Fe3+:

Add dilute NaOH:

OH- (aq)
[Fe(H2O)6]2+ (aq) Fe(OH)2 (s) green precipitate
 OH- (aq)
[Fe(H2O)6]3+ (aq) Fe(OH)3 (s) brown precipitate

To distinguish between the two:

(i) Add dil. NaOH (See above reactions)

(ii) Add a weak base (e.g. Na2CO3) (See ‘Acid-base behaviour of transition metal ions’ above)

(ii) Add potassium thiocyanate (KSCN):

Fe3+ ions give a blood-red solution:

SCN- (aq)
[Fe(H2O)6]3+ (aq) [Fe(H2O)5SCN]2+ (aq) blood-red solution

Fe2+ ions do not react with SCN- (aq).

➢ Crystal-Field Theory

This theory is used to explain the bonding in transition metal complexes and helps to account for
many of their observed properties.

Consider what happens when a ligand bonds to a central metal ion:

The driving force for the formation of a transition metal complex is the electrostatic force of
attraction between the positively-charged metal and the negatively-charged ligand. The complex
that results is lower in energy (and therefore more stable) than the separate metal ion and ligands.

However, although the positively-charged metal is attracted to the ligands, the ligands
themselves experience repulsion between their electrons and the d-orbitals of the central
metal ion.

For the purposes of the Crystal-Field Theory, ligands can be envisioned as negative points
of charge which repel d-orbitals.
There are 5 degenerate d-orbitals: dxy, dyz, dxz, dx2-y2, dz2

dx2-y2 – lobes lie on the x & y-axes

dz2 – lobes lie on the z-axis

dxy, dyz, dxz – lobes lie between two axes e.g. dxy – lobes lie between the x & y-axes

Therefore when a ligand approaches a central metal ion (on the way to complex formation), two
events occur:

1) The average energy of all the d-orbitals increases as a result of the mutual repulsion
with the electrons of the incoming ligand. All 5 d-orbitals are raised in energy by the
same amount.
2) Some of the individual d-orbitals experience a different increase in energy as compared
to the others, depending upon the geometry of the complex.
Consider an octahedral complex in which the 6 ligands coordinating to the central metal ion are
approaching along the x, y and z-axes.

The dx2-y2 & dz2 orbitals whose lobes are oriented/ lie directly along the path of the ligands will
experience a much greater extent of repulsion and hence a greater increase in energy as
compared to the dxy, dyz & dxz orbitals.

dx2-y2 & dz2 are called the e set of orbitals

dxy, dyz & dxz are called the t2 set of orbitals

This gives rise to Δ – the crystal-field splitting energy or ligand-field splitting energy.

This Δ value gives the magnitude of the energy difference between the e set of orbitals (dx2-y2
& dz2) and the t2 set of orbitals (dxy, dyz & dxz).

This Δ value also gives the magnitude of the energy of a photon in the visible light spectrum.

Supplying energy equal in value to Δ can cause a transition or promotion of an electron from a
(lower energy) t2 orbital to a (higher energy) e orbital.

(N.B.: This is how ‘transition metals’ got their name.)

e.g. Consider: [Ti(H2O)6]3+

Ti3+ = [Ar] 3d1 4s0 i.e. there is 1 electron in the d-orbital

 Δ

If the complex is irradiated with light of energy = Δ, a 3d electron is promoted.

Since this promotion involves d-orbitals, it is also referred to as a d – d or d→d transition.

The energy supplied can be related to the wavelength of the photon of light:

E = hν = hc where E = Energy (J)

λ h = Planck’s constant (6.63 x 10-34 Js)
c = speed of light (3.0 x 108 ms-1)
ν = frequency (s-1)
λ = wavelength (m)

The magnitude of Δ depends on:

➢ The transition metal itself

➢ The ligand

The ability of a ligand to cause an increase in the energy difference can be determined by
reference to the spectrochemical series:

CN- > CO > NO2- > en > NH3 > H2O > OH- > F- > SCN- > Cl- > Br-

Strong-field ligands Weak-field ligands

e.g. Because NH3 is a stronger ligand than H2O, a larger value of Δ is produced in complexes
containing NH3 than H2O.
e.g. Consider the following Cr(III) species:

Δ Δ Δ
Δ

N.B.: A larger value for Δ means that a shorter wavelength of energy is absorbed.

➢ Color

Objects exhibit color if they reflect (i.e. do not absorb) some or all of the wavelengths of light in
the visible spectrum (400 – 750 nm).

An object will appear black if it absorbs all the light in the visible region, and white if it absorbs
none.

For transition metal complexes, a complex will absorb visible light only if the wavelength of
that radiation corresponds to the energy required to promote a ‘d’ electron from the
ground state (e.g. the t2 set) to the higher energy state/ orbital (e.g. the e set).

In other words, when a compound is colored, it means that an electron has been promoted from
the lower energy set of d-orbitals to the higher energy set of d-orbitals, and a certain amount of
energy (i.e. Δ) must be absorbed to do this.
e.g.

Consider the color wheel:

A complex exhibits color when it absorbs a wavelength of light corresponding to a

complementary color (i.e. the color opposite to that color on the wheel).

In other words, the particular energy of radiation (i.e. visible light) that a complex absorbs
dictates the color that it exhibits.

e.g. If a complex absorbs light of wavelength 465 nm, this falls within the blue region of the
color wheel. The complex will then appear as a color complementary to blue (i.e. opposite to
blue on the color wheel). Therefore, the complex will be orange.

e.g. A complex absorbs light of radiation 500 nm. What is:

(i) The color of the complex?

(ii) The energy change that occurs when the complex absorbs visible light?
(i) Since the complex absorbs light in the green region of the spectrum, it will appear red.

(ii) 500 nm = 500 x 10-9 m = 5.00 x 10-7 m [1 nm = 10-9 m]

E = hc
λ

E = (6.63 x 10-34 Js)(3.0 x 108 ms-1) = 3.98 x 10-19 J

5.00 x 10-7 m

Note that this E value is the energy change for one (1) particle (photon) of light or in this case,
one (1) complex molecule. For a mole of particles or molecules, the energy change will be:

E for 1 mole = E x L = (3.98 x 10-19 J) x (6.022 x 1023) = 240 kJ mol-1

In order to absorb light, the metal ion has to contain not only at least one ‘d’ electron but also a
space in the higher d-orbital. The absence of color in Sc3+, Cu+ and Zn2+ compounds is due to the
fact that they have either no ‘d’ electrons (Sc3+) or a d10 arrangement (Cu+, Zn2+). In these cases,
no d→d transition is possible. (Recall: These ions are not considered transition metal ions.)

➢ Magnetism

Apart from their industrial importance, the magnetic properties of transition metal complexes
yield important information about the nature of their bonding and electronic configuration.

Complexes have electrons. Each electron has a ‘spin’ (whether up or down) which confers upon
it a magnetic moment. This results in an electron behaving like a tiny magnet. Therefore, the
magnetic property of a complex is directly related to the number of unpaired electrons in
its structure.
Types of Magnetism:-

▪ Diamagnetism:

In diamagnetic complexes, all of the electrons are paired in their orbitals and hence the ‘up’
spins cancel out the ‘down’ spins, giving no net magnetic moment.

Diamagnetic complexes are generally described as being non-magnetic. However, when placed
in a very strong magnetic field they will actually experience a slight repulsion with the field.

▪ Paramagnetism:

Complexes which have at least 1 unpaired electron in their orbitals exhibit paramagnetism.
They will therefore possess a net magnetic moment and hence will be strongly attracted to a
magnetic field. When placed in a magnetic field, the magnetic moments become aligned parallel
to each other thus they are drawn/ attracted to the field.

▪ Ferromagnetism:

The electron spins in certain complexes are aligned in a particular (i.e. same/ parallel)
direction even in the absence of a magnetic field, i.e. they remain aligned/ parallel when the
field is removed.

This is in contrast to paramagnetic complexes where in the absence of a magnetic field, the spins
of the unpaired electrons are randomly oriented once again. They only align in the presence of
the field.

Ferromagnetic complexes are therefore considered to be Permanent Magnets.

Among the transition elements, the only ones that are ferromagnetic are Fe, Co and Ni.

As indicated by the Crystal-Field Theory, the type of ligand present (i.e. strong-field vs.
weak-field) needs to be considered when determining the color and magnetic properties of
complexes.

(Recall: The type of ligand influences the value of Δ.)

 CN- is a strong-field
ligand and produces a
larger value for ∆.

F- is a weak-field
ligand and produces a
smaller value for ∆.

Paramagnetic Diamagnetic

➢ Electronic configuration in octahedral complexes

Recall that in octahedral coordinate geometry, there is the higher energy e set of orbitals (dx2-y2
& dz2) and the lower energy t2 set of orbitals (dxy, dyz & dxz).

Electrons are filled into these orbitals as follows for up to 3 electrons:

e.g.
From Hund’s Rule, we expect that electrons will always occupy the lowest-energy vacant d-
orbitals first. Electrons are filled in singly and with the same spins. This is very simple if there
are only 3 ‘d’ electrons.

However, a problem arises when a 4th electron has to be put in:

Does this electron go into the e set or the t2 set of orbitals?

If the crystal-field splitting energy (∆) is high, i.e. if it requires too much energy to promote the
extra electron to the higher energy e orbital than to leave it in the lower energy t2 orbital:

Then the electron will go into the t2 set, i.e. spin-pairing of electrons occurs.

The complex is then described as ‘low spin’, where electrons are arranged so that they remain
paired as much as possible.

If the crystal-field splitting energy (∆) is low, i.e. if it requires very little energy to promote the
extra electron to the higher energy e orbital:

Then the electron can be placed in the e set, i.e. promotion/ transition of electrons occurs.

The complex is then described as ‘high spin’, where electrons are arranged so that they remain
unpaired as much as possible.

Electronic configuration depends on:

➢ The type of ligand (strong-field vs. weak-field)

➢ The number of ‘d’ electrons (which in turn depends on the oxidation state of the metal
ion)
e.g. (1) Consider the two complexes: [CoF6]3- and [Co(CN)6]3-

Determine their electronic configurations.

Co is in the +3 oxidation state therefore it contains 6 electrons in its ‘d’ orbitals:

Co – [Ar] 3d7 4s2 Co3+ – [Ar] 3d6 4s0

F- is a weak-field ligand (which produces a lower Δ value) while CN- is a strong-field ligand
(which produces a higher Δ value).

Therefore, the following orbital-splitting diagram can be drawn:

Since Δ is smaller for

[CoF6]3-, electrons are
promoted rather than
spin-paired.

Since Δ is larger for

[Co(CN)6]3-, electrons
are spin-paired rather
than promoted.

Electronic configuration of octahedral complexes helps us to determine the number of

unpaired ‘d’ electrons present in its orbitals.
e.g. (2) How many unpaired electrons are there in [CoF6]3- and [Co(CN)6]3- ?

(Refer to e.g. (1))

There are 4 unpaired electrons in [CoF6]3- and no unpaired electrons in [Co(CN)6]3- .

e.g. (3) How many unpaired electrons are there in [Fe(H2O)6]2+ and [Fe(CN)6]4- ?

Fe is in the +2 oxidation state therefore it contains 6 electrons in its ‘d’ orbitals:

Fe – [Ar] 3d6 4s2 Fe2+ – [Ar] 3d6 4s0

H2O is a weak-field ligand (which produces a lower Δ value) while CN- is a strong-field
ligand (which produces a higher Δ value).

Therefore, the following orbital-splitting diagram can be drawn:

4 unpaired electrons no unpaired electrons

➢ Electronic configuration of tetrahedral complexes

Most 4-coordinate complexes have a tetrahedral geometry. (The most efficient way for 4 ligands
to bond to a central metal ion is by approaching from the vertices of a tetrahedron.)

In tetrahedral complexes, the splitting of the d-orbitals is exactly opposite to the splitting in
octahedral complexes: the higher energy set of orbitals is the t2 set (dxy, dyz & dxz) and the
lower energy set of orbitals is the e set (dx2-y2 & dz2).
 t2 set

E Δ
Metal ion plus
ligands
e set

In tetrahedral crystal field

Free metal ion

Because there are only 4 ligands bonded to the central metal ion, then regardless of the identity
of the ligands, the crystal-field splitting energy (Δ) will always be small. That is, electron
promotion will always occur before any spin-pairing of electrons.

Therefore, all tetrahedral complexes tend to be high-spin.

e.g. high-spin