Cl

Si Cl O
Cl H
Cl H

Title: D-BLOCK ELEMENTS

INTRODUCTION

D-block elements are between group II and III on the periodic table. These elements have properties
similar to those of S-block and P-block. These elements form ionic as were as covalent compound.

The elements are useful in the manufacture of tools, electric cables, jewelleries and are also
important in biological system as catalyst (enzymes), oxygen transport (haemoglobin, `myoglobin). Some
of the elements can be used as food supplement.

What are d-block elements and transition elements?

D-block elements are those elements whose valence electrons are entering the inner d-subshell.
The first d-block series are from scandium to zinc
Elements symbol Atomic Electronic configuration
55
 number
Scandium Sc 21 [Ar]3d14s2
Titanium Ti 22 [Ar]3d24s2
Vanadium V 23 [Ar]3d34s2
Chromium Cr 24 [Ar]3d54s1
Manganese Mn 25 [Ar]3d54s2
Iron Fe 26 [Ar]3d64s2
Cobalt Co 27 [Ar]3d74s2
Nickel Ni 28 [Ar]3d84s2
Copper Cu 29 [Ar]3d104s1
Zinc Zn 30 [Ar]3d104s2
Why in transition, electrons are removed from the 4s before the 3d whereas the 4s orbital is lower in
energy than the 3d (according to aufbau principle)
NB: The 4s-orbital is lower in energy than the 3d-orbital (aufbau principle) but the 3d-orbital is nearer the
nucleus than the 4s-orbital. This is because when an electron enters the 3d-orbital it repels the 4s-
elecctrons to a higher energy level. Therefore electrons are removed from the 4s before the 3d.
Why is the electronic configuration of chromium [Ar] 3d54s1 and not [Ar] 3d44s2?
 this is because half filled 3d5 and 4s1 orbital(according to Hund’s rule) are more stable than partially
filled 3d4 and completely filled 4s2-orbital

Explain why the electronic configuration of copper is 3d104s1 and not 3d94s2

 this is because completely filled 3d10 and half filled 4s1 orbital are more stable than partially filled 3d9
and completely filled 4s2 orbital

Electrons in boxes for d-block elements

3d 4s 3d 4s
Sc Ar Fe Ar
3d 4s 3d 4s
Ti Ar Co Ar
3d 4s 3d 4s
V Ar Ni Ar
3d 4s 3d 4s
Cr Ar Cu Ar
3d 4s 3d 4s

Mn Ar Zn Ar

Electronic configuration for some ions in the d-series

56
 3d 4s 3d 4s
Sc Ar Mn Ar
3d 4s 3d 4s
Ti Ar Fe Ar
3d 4s 3d 4s
V Ar Fe Ar
3d 4s 3d 4s
Cr Ar Cu Ar
3d 4s 3d 4s
Mn Zn Ar
Ar

Exercise: calculate the oxidation state of each d-element in the compound below and use box notation to
write the electronic configuration

i) ii) iii) (iv) (v)

Which is more stable? . is more stable than because has a half filled 3d
orbital which is more stable than a partially filled 3d-orbital in

It is easier to oxidise to but difficult to oxidise explain. This is

because has partially filled 3d which is less stable, thus less energy is required removed an electron
to make with more stable half filled 3d-orbital.but is half filled and more stable thus much
energy is required to remove an electron from to make with a less stable partially filled 3d-
orbital.

Scandium and zinc are d-block elements but are not transition elements explain

Transition elements: These are elements which form at least one stable ion with a partially or incomplete
filled d-subshell (orbital).

 Sc and Zn are d-block elements but are not transition elements because; scandium form only one stable
ion with an empty d-orbital while Zn forms only one stable ion with a completely filled d-
subshell. (see electron in boxes for some ions above). This explains why scandium and zinc do not form
variable oxidation state, their compounds are white in colour unlike transition metal compounds which are
coloured, scandium and zinc show little catalytic activities, they are usually diamagnetic whereas
transition metal compounds are paramagnetic or diamagnetic.
Therefore transition elements are from Ti to Cu.

Physical properties of transition element

i) Atomic radius: It decreases from scandium to copper because of increases in effective nuclear charge.
The decrease is only slightly because electrons are being added to the inner d-orbital which shield the
outer s-electrons much more effectively from the increasing nuclear charge.
 The flattening of the curve from vanadium to cupper is due to minimum volume occupied by atoms.

57
  The increase in atomic radius from Cu to Zn is due to shielding of outer S-electrons from completely filled
d-electrons.

Atomic radius nm

Sc Ti V Cr Mn Fe Co Ni Cu Zn
ii) Ionisation energy: the first ionisation energy increases from scandium to zinc because of increase in
effective nuclear charge and decrease in atomic radius. The increase is only slightly because electrons are
added to the inner d-orbital which shield the outer s-electrons much more effectively from increasing
nuclear charge.
l mo
First ionistion energy /kJ

Sc Ti V Cr Mn Fe Co Ni Cu Zn
The minor peak and trough are due to stability achieved due to half filled or completely filled orbital.
iii) Melting and boiling point: The melting and boiling point of transition element is higher than those of s-
block because of increase in the strength of metallic bond and decrease in atomic radius.
 Melting point increases from scandium to chromium due to increase in the strength of metallic bond
because of an increase in the number of unpaired electrons.
 Melting point decreases from iron to Zinc because of less availability of paired electrons in metallic
bonding.
 The melting point of manganese is less than that of chromium because the half filled 3d-electrons and
completely filled 4s-electrons in manganese are less available for metallic bonding.

58
 melting point / C

Sc Ti V Cr Mn Fe Co Ni Cu Zn
Characteristics of transition elements (metals)
a) They have variable oxidation state
b) The form complex ions
c) They form coloured compounds
d) They have catalytic activities
e) They are paramagnetic and diamagnetic in some of their compounds
a) Variable oxidation state
Why do transition elements have more than one oxidation state?
With the exception of scandium and zinc, all transition elements have variable oxidation state because the
3d and 4s electrons are similar in energy and can be used in bonding.
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Oxides Sc
Ti O V O Cr O
TiO V O CrO
MnO FeO CoO NiO CuO
Cu O
ZnO
MnO Fe Co O
Cr O Mn
MnO
Mn2O6
Chloride TiCl CrCl MnCl FeCl CuCl
ScCl TiCl VCl CrCl MnCl FeCl CoCl NiCl CuCl ZnCl
Common oxidation state
7
6 6 6
5 5 5 5 5
4 4 4 4 4 4 4
3 3 3 3 3 3 3 3 3
2 2 2 2 2 2 2 2 2
1 1 1 1 1 1 1 1
most stable oxidation state are in bold
Observing the table of oxidation state above it shows that the oxidation state of most elements is +2 or +3
or both. From the table it is also observed that the +3 is common at the beginning of the series while the
+2 is common toward the end.
Question: why is the +3 oxidtion state common at the beginning of the transition series while the +2 is
common toward the end? This is because across the series, there an increase nuclear charge which binds
the d-electrons more tightly hence only the weakly held 4s electrons are involved in bonding.

59
  From the table it is also observed that the maximum oxidation state of each transition element is equal to
the number of unpaired electrons in the d-subshell plus those in the s-subshell. This maximum oxidation
state increases from scandium to manganese.

Why will manganese exhibit +7 oxidation states? This is because manganese has a total of 7 electrons in
the 3d and 4s which are similar in energy and are used in bonding. OR all the electrons are
similar in energy and are used in bonding.

The maximum oxidation state is not attained from iron to zinc. This is because of decrease in the number
of unpaired electrons and increase in nuclear charge which binds the 3d-electrons more tightly. Hence
only the weakly held 4s electrons are involved in bonding.

 Transition elements exhibit their highest oxidation state with the most electronegative elements like
fluorine and oxygen.
 Ti, V, Cr. Mn never form simple ionic compounds in their highest oxidation state. This is because the
metal ion will be highly charge and small and will turn to polarise the anion. Thus compounds of these
elements in their highest oxidation state turn to be covalent (eg etc.
b) Formation of complex ions
What is a complex ion? This is a metal ion surrounded by an anion or with neutral molecule with a lone
pairs of electron called ligand.
A ligand: A ligand is an anion (negatively charge ion) or a neutral molecule with at least a lone pair of
electrons which can be donated to the central metal ion (CMI) to form a dative (coordinate) covalent
bond.
Most ligands are Lewis bases (nucleophile = electron pair donor) while the central metal ion is n Lewis
acid (electrophile=electron pair acceptor).

Why would transition elements form complexes? This is because the elements are small and highly
charge with the availability of low lying d-subshell (orbital) for dative covalent bond formation. In
complex formation, the lone pairs of electrons on ligands are donated to the vacant d-orbital of the
transition metal ion.

 The coordination number of metal in a complex is “the number of dative bond the central metal ion can
form with the ligands.” E.g consider the complex tetraamminecopper(III) ion ( ) the
coordination number of copper in the complex is 4
Some complexes and their coordination number
Complex Coordination
number
6
6
2
5
4
6
6
6
60
 6
NB: en = (ethane-1,2-diamine or ethylenediamine, or 1,2-diaminoethane)

Types of complexes

i) Anionic complex: It is a complex with an overall negative charge e.g ,

.
ii) Cationic complex: It is complex with an overall positive charge e.g

iii) Neutral complex: It is a complex with an overall charge of zero.e.g ,

Types of ligand.

i) Monodentate ligand: These are ligands which donate only one lone pair of electron using one donor
atom to the centre metal ion to form a single coordinate (dative) bond. E.g

ii) Bidentate ligand: These are ligands which donate two lone pairs of electrons using two donors atom to
the centre metal ion to form two coordinate (dative) bonds. E.g.
.
O
C
O
O OH
O
C C
O O
oxalate ion or ethanedioate ion 2-hydroxylbenzoate
H2NCH CH NH
ethane-1,2-diamine or
1,2-diaminoethane or
ethylenediamine (en)
iii) Polydentate ligand: These are ligands which donate more than two lone pairs of electrons using more
donor atoms to the centre metal ion to form more dative bonds. E.g. Ethylenediaminetetraactate (EDTA).
EDTA is a hexadentate ligand.
O O

O C CH CH2 C O
N CH2CH2 N
O C CH2 CH2 C O
O O
EDTA (Ethylenediaminetetraacetate)
Bidentate and Polydentate ligand are referred to as chelating ligand.

61
 What is a chelating ligand? This is a ligand which can form ring structure together with the centre metal
ion. The complex form between chelating ligand and metal ion is called chelate (or chelating complex).
E.g tris(ethylenediamine)cobalt(III) ion.
3+
CH2CH2
H
NH
H CH en
2 CH
2 en
Co

HN Co
H NH
en
CH2CH2 =

The charge of a complex

The charge of a complex is the algebraic sum of the charge of a ligand and that of the central metal ion.
The charge of a complex containing a neutral ligand is simply the charge carried by the central metal ion.

 For example, consider a complex formed between chromium(III) ion and water as in
The overall charge of the complex is +3 because water is a neutral ligand.
 Consider the complex formed between chromium(III) ion , water, and chloride ion ( ) as in
. The overall charge of the complex is -1 ie
. Only chloride ions affected the overall charge as there are 4 chlorine atoms in the
complex.
Some neutral ligands are H2O, NH3, CO, ethylenediamine (1,2-diaminoetthane OR ethane-1,2-diamine),
NO

Calculating the oxidation state of the centre metal ion in a complex.

The same rule for calculating the oxidation state of an element in a compound is followed.
The table below shows some ligands and their net charges
Ligand Net charge
i) All -1
halogens( ,
ii) -2
iii) EDTA -4
iv) H2O, NH3, CO, NO, en (ethylenediamine) 0
 Calculate the oxidation state of the transition metal in the complex below
a) [Cu(CN)4]2- b) [Cr(H2O)3Cl3] c) K4[Fe(CN)6] d) [Co(NH3)6]Cl3
Solution

62
 Calculate the oxidation state of the central metal ion in the complex below
[Cr(en)3]3+, [Co(Cl)3Br3]3-, [Co(NH3)5(SO4)]Br
Naming complexes
i) Determine the overall charge of the complex if it is not given. This will help you to know if you are
dealing with a cationic complex or anionic complex or neutral complex.
ii) Name the cation first before the anion.(ie name the cationic complex first before the anion attach to it OR
the cation attach to an anionic complex first)
iii) Identify the ligand. The name of anionic ligand(negative charge ligand) end with O e.g
Anion formula Name of ligand
Fluoride Fluoro
Chloride chloro
Bromide bromo
Iodide iodo
cyanide cyano
*Thiocyanate Thiocyanato (ligand bond using S-atom)
isothiocyanato (N)) (ligand bond using N atom)
Hydroxide Hydroxo
Oxide oxo
Carbonate carbonato
Sulphate sulphato
Oxalate oxalato
Nitrate nitrato
*nitrite Nitro(ligand bond to CMI using N atom))
nitrito (ligand bond to CMI using O-atom)
EDTA See structure ethylenediaminetetraacetate
above
acetate acetato
*the ligand is an ambidentate ligand: these are ligands which can bond to the centre metal ion through
one atom or another atom
iv) State the number of ligands of the same kind around the central metal ion using the greek prefix, di, tri,
tetra, penta, hexa, hepta, octa, nona, deca etc followed by the specific name of the ligand.
v) If the name of the ligand contain a greek prefix like in: ethylenediamine (or 1,2-diaminoethane or ethane-
1,2-diamine), and ethylenediaminetetraacetate(EDTA), use bis(2), tris(3), tetrakis(4), to indicate the
number of ligands, followed by the name of the ligand in bracket
vi) Neutral ligands are usually given the name of the molecule except with: water, ammonia,
Name formula Name of ligand
water H2O aqua
ammonia NH3 ammine
carbon monoxide CO carbonyl
Nitrogen monoxide NO nitrosyl
vii) If the complex is a cationic complex, the English name of the central metal ion is used
 If it is an anionic complex, the suffix ate is added to the name of the metal. But if the centre metal ion has
a Latin name, the Latin name is used followed by the suffix ate. Except for mercury.e.g
63
 English name Latin name Name of metal if it is an anionic complex
Chromium Chromate
Cobalt Cobaltate
copper Cuprum Cuprate
Iron Ferrum Ferrate
Nickel Nickelate
Silver Argentums Argentate
Titanium Titanate
Vanadium Vanadate
Zinc Zincate
viii) Determine and indicate the oxidation state of the central metal ion in bracket using roman numerals. Do
not separate the name of the metal from the oxidation state. E.g Copper(III), Manganese(VII)
ix) Write name of the ligands, the name of the central metal ion, the oxidation state of the central metal ion
in that order as one word. E.g tetraaquadichlorocobalt(III) ion [Co(H2O)4Cl2]+
x) When there are two or more ligands of different kinds in a complex, write them in alphabetical order
without considering the greek prefix di, tri, tetra, bis, tris, tetrakis, etc.
xi) Note that a complex is always written in square bracket except in situation where oxygen and chorine are
the only ligand bonded to the metal ion. Any element outside the square bracket is separated from the
name of that complex.
xii) When writing the formula of a complex from it name, anionic ligands are written first before. neutral
ligands (either case is still accepted)
Examples
(a) Name the complexes below
i)
ii)
iii)

iv)
v)

Example 2

Give the IUPAC name of each of the following complex

(a)
Solution
The cation is listed first in a formula
(a) K [Fe CN ]
cation anion There are four potassium cations, thus the charge on the anion is -4. The
oxidation state of iron is . Hence the name of the complex is:
Potassium hexacyanoferrate(II)

64
 (b) [Cr(H O ]Cl
Cation anion
There are three chloride anions, so the charge on the cation is +3. The
oxidation state of chromium is . Thus the name of the complex is:
hexaaquachromium(III) chloride
(c) tetraamminedibromochromium(III) chloride. [verify the name using the method in (a) and (b)]
(d) dichlorobis(ethylenediamine)cobalt(III) cyanide OR bis(1,2-diaminoethane)dichlorocobalt(III)
cyanide OR dichlorobis(ethane-1,2-diamine)cobalt(III) cyanide.
Example 3
Write the structural formula corresponding to the following names:
(a) chloroethylenechromium(III) sulphate
(b) pentachlorotitanate(II) ion
(c) pentaamminesulphatocobalt(III) bromide
(d) potassium diamminedisulphatochromate(III).
Solution
(a) the complex cation chloroethylenechromium(III) is Cr 3+ with one chloride of charge -1, thus the
charge of the complex cation is -1+3=+2.sulphate anion of charge -2. Hence the formula is
the fomula then give [Fe(en)Cl]SO4
(b) overall charge of the complex is -5+2=-3, thus the formula of the complex is
(c) Overall charge of complex is 5(0)+-2+3=+1. Bromide has a charge of -1 the formula of the complex
is which then gives
(d) Overall charge of complex anion is 2(0)+2(-2)+3=-1. The cation which is potassium has a charge of
+1 thus the complex is which then gives .
Assignment
(a) Give the formula of the following complex
i) Potassium ethylenediaminetetraacetatecuprate(II)
ii) Bis(ethylenediamine)nickel(II) bromide
iii) Sodium trioxalatocobaltate(III)
iv) pentacarbonyliron(0)
v) ammonium aquapentachloroferrate(III)
(b) Name the complex below
i)
ii)
iii) .

SHAPES OF COMPLEX IONS

i) Octahedral complexes.

Octahedral complexes have coordination number of 6. The central metal ion is d 2sp3 or sp3d2 hybridised.
E.g

, , , ,
etc

65
 CN CN HO
NC NC
CN CN HO O

Cr Cr Fe

NC NC
CN CN HO OH
CN CN HO
[Cr(CN ] [Cr(CN ] [Cr(H O ]

O N
H H HH H
C O N C– O O
carbon monoxide Cyanide ion S
V-shape or bent shape trigonal pyramidal
bond angle 104.5 O O
bond angle 107 Structures of some ligands
sulphate ion

NB: EDTA is a hexadentate ligand, when complex to any central metal ion the shape is octahedral.

ii) Tetrahedral complexes

Tetrahedral complexes have coordination number of 4. The centre metal ion is sp 3 hybridised or d3s
hybridised. E.g

NH Cl
CO

Zn Co
Ni

HN NH Cl Cl CO OC
HN Cl CO
[Zn(NH ] [CoCl ] [Ni(CO) ]

Tetrahedral complex are very common with larger negative charge ion like Cl-.

iii) Square planar complexes: Square planar complexes also have a coordination number of 4 but the central
metal ion is dsp2 hybrdised with a d8 arrangement of electrons. There are only few 4 coordinate complexes
that are square planar. E.g

CN
NC NC CN

Ni Co

NC NC CN
CN

66
iv) Linear complex

A complex with coordination number 2 is a linear complex.

HN Ag NH

ISOMERISM IN COMPLEXES.

What is an isomer? These are compounds with same molecular formula but different structural
arrangement.

 Complex ions have two main types of isomerism, namely structural isomerism and stereoisomerism
a) Structural isomerism .This isomers differ in the way the ligands are bonded to the central metal ion. The
different types of structural isomers are:
i) Ionisation isomerism: The ligand inside the coordination sphere is exchange with those outside the
coordination sphere. The isomers differ in the ligand that is coordinated to the central metal ion.. E.g
 Pentaamminesulphatocobalte(III) bromide ,
 Pentaamminebromocobalt(III) sulphate

Question how can you distinguish the two isomers?

The two isomers above can be distinguished using acidified solution of or acidified solution of

will give a cream (pale yellow) precipitate with acidified with dilute but
no observation with acidified solution of while will give a white precipitate with
acidified with dilute HCl but no observation with acidified solution of
Other examples of ionisation isomerism are and . These two
isomers can be distinguished using acidified solution of or the brown ring test for nitrate. [READ
TEST FOR NITRATES]
ii) Linkage isomerism: The isomers differ only in the atom of the ligand which is bonded to the central
metal ion. For example a ligand like can bond to the central metal ion either with the electron pair on
the nitrogen atom or the electron pair on the oxygen atom as in the complex
and . The structures are shown below.

ONO NO

HN NH H N NH
Cl Cl
Co Co

H N NH
HN NH

NH
NH
pentaamminenitritocobalt(III) chloride pentaamminenitrocobalt(III) chloride

67
 N N
O O O
O
Resonance structures of nitrite ion
A ligand that can bond through one atom or another atom to the central metal ion is called an ambidentate
ligand. E.g . Can bond to the central metal ion through nitrogen atom or sulphur
atom.
iii) Hydration (hydrate) isomerism: it is another type of ionisation isomerism whereby the isomers differs
only in the way water ligand inside the coordination sphere is exchange with other anionic ligand outside
the coordination sphere.
A well studied example is as shown below
A. Hexaaquachromium(III) chloride
B. Pentaaquachlorochromium(III) chloride
C. Tetraaquadichlorochromium(III) chloride
Question how can the isomers above be distinguished
 In the violet complex (A) all the water molecules are coordinated to the chromium atom. That is all the
water molecules are inside the coordination sphere.
 In the light green (B) and dark green (C) complex, one or two water molecules are not directly
coordinated to the chromium atom but occur outside the coordination sphere.
 The 3 isomers A, B, C can be distinguished by conductivity method (to determine the number of
ions per formula) OR by precipitation titration using acidified solution of
 The three isomers loses different amount (number of moles) of water molecules when exposes to dry
atmosphere in the presence of conc . (A dehydrating agent). Only the water molecules outside the
coordination sphere will be removed by conc . Also only the chloride ion outside the coordination
sphere will give a white precipitate with acidified solution of
iv) Coordination isomerism: The isomers are consisting of a complex anion and a complex cation that
differs in the way the ligands are distributed between the metal atoms in the complex. E.g
A.
B.

Question: what are the differences in the structures above?

 In A, ammonia and cyanide interchanges their metal ions. So to in B where chlorine and ammonia
interchanges the metal atoms.
It is also possible for the ligands to be distributed in different ways between two metal atoms of the same
element. E.g
b) Stereoisomerism
These are isomers in which the complex have the same molecular formula but differ in the spatial
(precise) arrangement of the ligands in space around the central metal ion. There are two types of
coordination isomerism, namely: Geometric and Optical isomerism.
i) Geometric isomerism (or cis-trans isomerism). The ligands are bonded to the central metal ion in the
same way but there is a restrict rotation about a particular bond type.
 The term cis and trans are use to distinguished between two geometric isomers.
 The term cis means two atoms or group of atoms are adjacent to each other in the structural formula while
trans means the atoms or group of atoms are opposite to each other in the structural formula
68
 Geometric isomerism will not occur in tetrahedral complexes but will occur in square planar (MB2A2)
and octahedral complexes (MA4B2) (M=metal ion, A and B are different ligands). E.g

H N Cl NH
Cl

Pt Pt

H N Cl H N Cl
cis-diamminedichloroplatinum(II) trans-diamminedichloroplatinum(II)
orange yellow pale yellow

[Co(NH ) Cl ]

Cl +
NH +

H N N
Cl N
Co
Co
H N NH
Cl NH

NH Cl
cis -tetraamminedichlorocobalt(III) ion trans -tetraamminedichlorocobalt(III) ion
Purple green

[Co(en) Cl ]
[Co(en) Cl ]

Cl +
en +

Cl
en
Co en
Co
Cl

en
Cl
trans -dichlorobis(ethylenediamine)cobalt(III) ion cis -dichlorobis(ethylenediamine)cobalt(III) ion
trans-bis(1,2-diaminoethane)dichlorocobalt(III) ion or cis-bis(1,2-diaminoethane)dichloro(III) ion

+
en

Cl

Co

Cl

en

trans -dichlorobis(ethylenediamine)cobalt(III) ion

trans-bis(1,2-diaminoethane)dichlorocobalt(III) ion

69
 H NCH CH en
How can you distinguish between the cis and trans isomer?
The cis and trans isomers can be distinguished by predicting their polarity.
The trans isomer is symmetrical and non-polar. Thus the trans isomer is slightly soluble in water.
The cis isomer is polar and more soluble than the trans.
Polarity is detected by a dipole moment. The trans has no dipole moment while the cis has dipole moment.

Question. Is there a geometric isomer of the stable octahedral complex if yes draw
the isomers

Draw the isomers of

ii) Optical isomerism. These are isomers which are non-superimposable on their mirror image.
 Optical isomers have the ability to rotate plane polarise light.
 Two isomers which are mirror images and are non-superimposable are called enantiomers
 An enantiomer which rotate a plane polarise light to left is said to be levorotatory (l or -) while
enantiomer which rotate plane polarise light to the right is said to be dextrorotatory (d or +)
 An equimolar mixture of two enantiomers is called a racemic mixture. This mixture do not rotate plane
polarise light.
 Only cis isomers are optically active.
E. g
en
en

Co
en en Co

en
en
cis cis
enantiomers
O Mirror O
C O O
O C
C O
C
O O
O O O
O
Fe C C
Fe
C C
O O O
O O
C O
O C O C
C O
O cis
cis- trioxalatoferrate(III) ion
O
enantiomers

70
 en
en
Cl
Cl
Co
Co

Cl
Cl
en
en
cis cis
enantiomers
Cl
Cl

H O Cl
Cl OH
Co
Co

H O Cl
Cl OH
H O
H
cis cis
enantiomers
 Optically active isomers are chiral. i.e isomers which are non-superimposable on their mirror image.
 Chiral molecules have a chiral atom. That is an atom which is bonded to four groups of atoms of different
kind.
 An isomers which is super imposable on it mirror image is said to be achiral. Achiral molecules are
optically in active. That is the isomer does not rotate plane polarise light
Stability of complexes
 The stability of a complex is the measure of the complex to undergo ligand substitution reaction. Ligand
substitution is an equilibrium reaction with an associated equilibrium constant (Kst).
 A stability constant expresses the interaction strength of a ligand relative to the interac-tion strength of the
solvent molecules (usually H2O) as a ligand
 A stepwise stability constant is the stability constant for each individual solvent replacement in the
synthesis of the complex; an overall stability constant is the product of the stepwise stability constants
Consider the reaction below
 When ammonia is added to a solution of nickel sulphate ( , there is a noticeable colour change
because some of the water molecules in are converted into ions.

 The concentration of water is taken as constant. The value obtained for the reaction above is

. The value is known as the stability constant for .Kst is always

quoted as
71
 The value quoted above for a Kst is the overall stability constant for the six step reaction of the reaction
above (Eqn*). Therefore, the Kst is obtained from

 The higher the stability constant, the more stable the complex.
 By comparing the stability constant, it is possible to know which ligand will displaced another in a
reaction. Eg consider the table below
Ligand EDTA
5.6 13.3 18.8 27.3
will displace all other ligands in a complex followed by EDTA will form a ring structure around the
central metal ions.
 A complex that will undergo rapid ligand substitution is referred to as a labile complex. Such a complex is
less stable. A non-labile complex will not undergo rapid ligand substitution.

Factors affecting the stability of a complex.

i) The size and charge of the central metal ion the higher the charge (higher the charge density) the
smaller the size of the central metal ion, the more stable the complex.
The nature of the ligand. A more basic ligand will form a more stable complex. Ligand which form a
ring structure around the central metal ion such as bidentate and Polydentate ligand form a more stable
complex.
The relative strength of ligand for a particular central metal ion is given on a spectrochemical series as
shown bellow. EDTA,> en,>CO,> CN -,> > S2-,> I-,> S2O32-,> Br-,> NH3,> Cl-,> OH-
A spectrochemical series is a series which arranges ligands in order of their abilities to split the d-
orbital energy of the central metal ion.
Case Study
A drop of NH3(aq)
Excess NH3(aq)
Consider the reaction scheme below

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 CuSO
white

CuCO drop of H O
Blue PPt
CO 2-
(aq) CuSO4 H2O drop of N aq)
pale blue
Cu OH Exc
Excess H2O pale blue ppt es sN
H(
3 a q)

CuCl excexcessCl
essconc HCl [Cu(H 2O)6]
2 OH Cu(OH)2
Excess NH3(aq)
Cu NH
Olive pale blue solution pale blue ppt deep blue solution
green or green excess S exce
solution ss S 2 excess S
excess Br CuS excess CN
dark brown ppt
excess S exces
s CN
CuBr Cu[(CN)
green solution
E xc e
ss ED EDTA
ss EDTA colourless solution
TA
exce
2-
Cu EDTA)

Determining the formula of (stoichiometry) of a complex. ions

The formula of any complex can be obtained by determining the number of ligands which are linked to the
central metal ion. This can be done by titration method or by Colorimetric method.

 Titration method. The titration method involves competitive complexing.

For example: when 20cm3 of 0.1M iron(III) chloride was added into a flask, a few drops of sodium 2-
hydroxylbenzoate were added a purple colour was observed. When 0.1M of EDTA was then added from a
burette and the solution became a clear yellow colour after addition of 20.1cm3. Calculate

i) How many moles of Fe3+ were taken

ii) How many moles of EDTA reacted with Fe3+
iii) How many moles of EDTA reacted with one mole Fe3+
iv) What is the formula of a Fe3+/EDTA
Solution
i)
ii)
iii)
iv) Formula

Colorimetric method. This method involves measuring the colour intensity of equimolar solution of the
central metal ion and ligand of various proportions. A graph of colour intensity of various mixtures is

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 plotted. The maximum colour intensity gives the colour of the complex formed which gives the molecular
formula of the complex

maximu colour intensity

n
io
opt
abs

0 2 10 volume of CMI
10 8 0 volume of
ligand

Uses of complex ions

i) EDTA is used medically to extract poisonous metal from the body fluid
ii) Aqueous EDTA is used in complexometric titration to estimate the concentration of aqueous metal ion
iii) Two important biomolecule are made up of complex ions e.g. haemoglobin and chlorophyll
iv) Some EDTA complexes are use as water softener.

c) Formation of colour compounds

Why transition metal complexes (solutions) are usually coloured?
Why the solutions of scandium and zinc compounds are never coloured?
What is the meaning of d-to-d transition and how does it happen?
Why is the solution of yellow while that of ?
2+
Why would Ni form a green ppt with NaOH but brown solution with excess dilute NH3(aq)
Copper is a transition metal why are some of it compounds white?
Most compounds or ions of transition metal are coloured. The colours of these compounds are associated
to an incompletely (partially) filled d-subshell. A compound will appear coloured if it absorbs light in the
visible region of the electromagnetic spectrum.
Transition metal complex or compound are usually coloured because associated ligand in the complex or
compound split the d-orbital into two energy levels. Promotion of unpaired electrons in the d-orbital
between the energy levels absorbs visible light of a particular wavelength. Thus the compound appeared
coloured.
How does the splitting take place? The d-orbital are degenerate orbital‟s (orbitals of exactly the same
energy). When a ligand approaches the five 3d-orbital, some of the orbitals are closer to the ligand than
orders. The ligand is considered as a point of negative charge which repelled the electrons in the orbital
thereby causing an alteration in the energy of the orbitals. Thus, orbitals closer to the ligand are repelled to
higher energy level. For example, in octahedral complex, three of the d-orbital ( are at
lower energy level while are at higher energy level.

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 radition

isolated atom or ion

with all the d-orbitals
having similar energy

the d-orbital is split the electron absorb

by a ligand but the electron radiation (energy
still in the gound state E=hv) and it is
promoted
to higher energy orbital

The splitting of the d-orbital is known as-orbital Ligand field splitting. An electron can be promoted from
a lower energy orbital to a higher energy orbital as the compound absorbs energy. These can only happen
if there is:
At least one electron in the d-orbital and there is a space in one of the orbital in the higher energy level.
The solution of scandium never coloured because: Scandium form only with an empty d-orbital. Thus
there is no electron to undergo d-to-d transition when the compound absorbed radiation of particular
wavelength in the visible region of EM spectrum.
Solutions of zinc are not coloured because zinc form with completely filled d-orbital. Thus no empty
d-orbital present at higher energy level for d-to-d transition of electron when the compound absorbs light
of particular wavelength in the visible region.
Solution of copper(I) are colourless because the d-orbital is completely filled and there is no orbital in the
higher energy level for d-to-d electron of transition to take place when the compound absorb light of
particular wavelength. This explains why some compounds of copper are colourless.

Three things that can result to a change in colour of transition metals are:

 Change in ligand: changing a ligand around the central metal ion changes the colour perceived. For
example. A pale blue solution of copper(II) sulphate turns do deep blue when excess aqueous ammonia is
added because the ligand around the central metal ion has change.
Cu(H O) + NH (aq) Cu(NH )
pale blue deep blue
 Ligand exchange and change in coordination number. Exchanging the ligand and coordination number
of the central metal ion causes a change in colour. For example a pink aqueous solution of cobalt(II)
chloride turns blue when excess conc.HCl is added because of exchange in ligand and coordination
number
.

Pink blue
Change in oxidation state. a change in oxidation state changes the colour perceived. Thus the colour of
yellow while that of because the oxidation state of chromium in the two
compounds are different.(+3 and +6)
Two transition metal ions will have different colours even when the two metal ions have the same
oxidation state or the same electronic configuration e.g Cu2+(blue) and Fe2+(pale green), Fe3+(brown)
and Mn2+(pale pink)
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 compounds colour Compounds Colour
KMnO7 Purple CuO black
K2Cr2O7 orange Cu brown
K2CrO4 yellow
CuSO4.5H2O Blue
FeCl3 Brown
NiCl2.H2O green

d) Catalytic activity of transition metals.

 What is a catalyst?
 Why are catalysts important in industrial processes?
 Why are most transition metals suitable as catalyst?
 Distinguish between a homogeneous and heterogeneous catalysis
 Give a reaction in each case to show how transition metals are used as homogeneous and
heterogeneous catalyst
A catalyst is a substance that speed up the rate of a chemical reaction without being permanently change at
the end of the reaction.
 Catalyst provides an alternative route of lowering the activation energy.
 Transition metal and their compound show catalytic activity because:
They have the ability to change from one oxidation state to another
They have a partially filled d-orbital

There are two main type of catalysis namely: homogeneous catalysis and heterogeneous catalysis

i) Homogeneous catalysis: The catalyst and the reactant are in the same phase (same physical state).
 Transition metals act as homogeneous catalysis because of the ability to change from one oxidation state
to another. In this way, they act as intermediary for the exchange of electron between the reactance. For
example the reaction between peroxodisulphate ) and iodide ion . The reaction is catalysed by

Fe2+(aq)
I aq S O aq aq SO aq
The reaction is much faster when iron(II) ion is used as a catalyst. The mechanism in the presence of a
catalyst is shown below.
S2O82-(aq) 2Fe (aq) SO aq Fe aq
Fe aq
I aq I aq 2Fe (aq)

verall equation= I aq S O aq aq SO aq

NB. The iron(II) ion only act to transfer electrons from iodide ion to peroxodisulphate
ii) Heterogeneous catalysis. The catalyst has a different phase (different physical state) with the reactant.
With few exceptions, the catalyst is usually a solid and the reactants gases. The catalyst adsorbs the
reactants onto its surface and hold close together favouring a good orientation.
 Transition metals are good as heterogeneous catalyst because

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 They can use their partially filled d-orbital to accept electrons density from adsorb molecule (reactants),
and thus change from one oxidation state to another. Hence formation of dative covalent bond. This
lowers the activation energy. For example
i) The contact process using vanadium(V) oxide as a catalyst or platinum.
V O
SO (g) O g) SO g)
Mechanism
SO (g) V O SO g) VO

VO (s) O (g)
V O s

overall SO (g) O g) SO g)

ii) The Haber process using finely divided iron as a catalyst

Fe
N (g H g) NH g)

iii) Hydrogenation of unsaturated hydrocarbons using nickel or platinum or palladium as catalyst

(manufacture of margarine from vegetable oil)
Ni
H C CH H (g) CH CH
C

iv) use to catalyse the decomposition of hydrogen peroxide

H O l MnO
H O(l) O (g)
v) Platinum rhodium used in the Oswald process for the manufacture of nitric acid

e) Paramagnetism most transition metals ions are usually paramagnetic. Paramagnetic substances are
weakly attracted by a magnetic field due to the presence of unpaired electron. The unpaired electrons spin
generating a magnetic moment. Paramagnetic property increases with increase in the number of unpaired
electrons. It reaches maximum in manganese(II) and Iron(III) which have five unpaired electrons while
least in scandium ion and Zinc ion which are diamagnetic due to lack of unpaired electrons.
Fe, Co, and Ni are strongly attracted to a magnetic field. Hence, they are said to be ferromagnetic.
Elements which are repelled by a magnetic a field are said to be diamagnetic. These elements have only
paired electrons.

More study questions

a) Give two physical properties of iron metal which show it to be a d-block element (2 marks) ans. High
melting point/high density/ very hard due to increase in metallic strength.
b) Give the formula of and shape of each of the complex formed when anhydrous cobalt(II) chloride is added
separately to water and to concentrated hydrochloric acid.
i) Give a reason for the difference in shape of the complex ions formed. In (b)
ii) Give a reason for the difference in colour in (bi) above
c) Ethylenediamine arc as a bidentate ligand. Deduce the formula of the complex ion formed when
cobalt(II)chloride is treated with an excess of 1,2 ethylenediamine in the absence of oxygen.
d) Copy the box below and give the electronic structure of the vanadium atom and
V Ar
3d 4s
V Ar

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 i) Suggest why the hydrate of is coloured
ii) Name the type of boning within ions of this type.(3 marks).
e) What properties of transition metals make them suitable as a catalyst
i) What is homogeneous catalyst
ii) What properties of transition metals make them suitable as a homogeneous catalyst
iii) The conversion of sulphur dioxide into sulphur trioxide, by the reaction with oxygen is catalysed by
industrial vanadium(V) oxide. Write equations to show the catalytic role of the vanadium(V) oxide in this
reaction.
f) State three characteristic properties of transition metals. Which of the property make transition metals
suitable as homogenous catalyst.
g) What is ligand? Distinguish between bidentate and Polydentate ligand. Give examples in each case.
h) Give three changes which can result in the in the change in colour during the reaction of transition metal.
i) Why are transition metals capable of forming complexes
j) Give the shape of the following complex

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