Department of Chemistry Lecturer and Tutor: Prof. R.C.

Jagessar

October/2023 CHM 3104 Prepared: Prof. R.C. Jagessar

History. Werner’s Theory. The Coordinate bond. Valence bond Theory (VBT). Crytsal Field
Theory

o A coordination compound is one that contains a central metal atom or ion surrounded by
a number of oppositely charged ions or neutral molecules known as ligands.
o Coordinate bond: Bond that is formed between a central metal and a ligand.
o Coordination number: This is the number of ligands attached to the central metal ion.
o Complex ion: When a group comprising the metal and its ligands carries a positive or
negative charge, it constitutes a complex ion.
o Each ligand molecule or ion has at least one pair of unshared electrons, which is donated
to the central metal to form a coordinate bond.
o The metal must have vacant orbitals of appropriate energy, which can accept these
electrons.
o Complexes are most commonly formed by transition metals and then the d –orbitals of the
penultimate quantum shell of the metal are generally involved in the bonding.
o For example, hexaminecobalt (III) chloride, Co(NH3)6Cl3 is a well known coordination
compound, readily prepared by the oxidation of an ammoniacal solution of cobalt (II)
chloride.
o The complex ion, [Co(NH3)6]3+ is made up of a tripositive cobalt ion and six ammonia
ligands, each nitrogen atom donating its lone pair of electrons to the metal.
o Water acts as a ligand in the same way as ammonia, because the oxygen atom can donate
one of its lone pairs to a metal.
o Many salts in aqueous solution and in the crystalline state contain metal ions complexed
(hydrated) with water molecules.

2+

NH3
NH3 NH3

Co

NH3 NH3
NH3

(aq)
Chelation: This is the ability of a ligand molecule to donate more than two electron pairs to the
central metal ion, resulting in the formation of a stereochemically stable complex. For instance,tris
(ethylenediamine) cobalt (III), formula (I), contains six (6) coordinate cobalt with each
ethylenediamine molecule, occupying two coordinate positions. In this complex, three rings which
each contain five atoms, have been established.
Chelate: This is also refer to as a complex.
Chelating agent: Those agents that are involved in the complexation process. They complex the
central metal ion.
 NH3 2+
NH3
NH3

Ni  = 108.6
Ni2+ (aq) + 6NH3 (aq) =

NH3 NH3 NH3

2+

NH2
H2N
NH2

Ni2+ (aq) + 3H2NCH2CH2NH2 (aq) =

Ni  = 1018.3
H2 N
H2N
NH2

• As a general rule, a complex containing one (or more) five or six membered chelate rings
is more stable (has a higher formation constant) than a complex that is similar as possible,
but lacks some or all of the chelate rings. A typical example is illustrated above.
• The complex with three chelate rings is about 1010 times more stable. This results from the
chelation effect. As with all questions concerning thermodynamic stability, we are dealing
with free energy changes (G°) and we first look at the contribution of enthalpy and
entropy, to see if one or the other is the main cause of the difference.
We can more directly compare these two reactions by combining them in the equation:
Ni(NH3)62+ (aq) + 3 (en) (aq) = Ni (en)32+ (aq) + 6NH3 (aq); (en= ethylenediamine)

For which
K = 109.7
G° = -RTlnK = -67kJ mol-1 = H°- TS
H° = -12 kJ mol-1
-TS° = -55kJ mol-1

• It is evident that both enthalpy and entropy favour the chelate complex, but the entropy
contribution is far more important.
• Data for a large number of these reactions, with many different metal ions and ligands,
show that enthalpy contributions to the chelate effect are sometimes favourable, sometimes
unfavourable, but always relatively small.
• The chelate effect is essentially an entropy effect.

• Chelate or complex: This is a complex that is formed from the union of a ligand and a
metal ion. Ligands can be monodentate, bidentate, tridentate, tetradentate, pentadentate,
hexadentate etc.

• Ligands or chelating agent; These are anions or neutral molecules that can be thought of
as electron pairs donors.

Types of ligands:
Monodentate: These are ligands that donate one electron pair to one central metal atom/ion.
They are also called, one-tooth ligand. These can be classified as anionic and neutral molecules.
In both cases, the molecule has one electron pair per molecule. Examples include, F-,Cl-, Br-, CN-
, OH- , NH3, H2O, CH3OH.
Bidentate: These are ligands that contain two or more atoms, each of which can simultaneously
form a two electron donor bond to the same metal ion.
 H2N NH2

CH2CH2
N N
ethylenediamine (en)

2,2'-Bipyridine (bpy)

P(H3C)2 P (CH3)2

CH2CH2

Bis(dimethylphosphino)ethane (dmpe)

N N

1,10-Phenanthroline (Phen)
O
O
H3C CH2CH2 CH3

Glyme

O O
-H+ O O O- O

H3C CH3 C C
H3C CH3 H3C CH3
H2

O O- O- O-
=
C C
H3C CH3 H3C CH3
H H
Tridentate ligands: These are ligands that have three electron pairs donors per molecule

N N

Tetradentate Ligands:
These are ligands that can donate four electron pairs per molecule. There are several tetradentate
ligands. These include Bis(dimethylglyoximato) ligand, triethylenetetramine. Also, Acacen.

O HO
CH3
H3C N N

N N CH3
H3C
O HO

Bis(dimethylglyoximato)

Hexadentate ligands: These are ligands that have six donor groups per molecule. A good example
is EDTA.
EDTA
 EDTA-Hexadentate complex
NOMENCLATURE FOR COORDINATION COMPOUNDS

The systematic IUPAC (International Union of Pure and Applied Chemistry) nomenclature for
complex compounds is summarized as follows:
1. The cation is always named before the anion.
2. The names of ligands precede that of the central ion.
3. The oxidation state of the central ion is denoted by Roman numerals in brackets
immediately after its name. To denote zero oxidation number 0 is used.
4. The stoichiometric proportions are denoted by Greek numerical prefixes (mono, di, tri,
tetra, penta, hexa, hepta and so on) in front of the names of the elements to which they
refer. The prefix mono is usually omitted. When it is necessary to indicate the number of
complete groups of atoms, e.g. the number of organic ligands coordinated to a metal atom,
the prefixes bis, tris, tetrakis etc. (2,3,4, etc.) are used.
5. Metals forming complex anions end in ate,whereas complex cations and neutral molecules
use their usual names.
6. The sequence for specifying ligands is: anions, neutral molecules and lastly cations. Within
each of these categories alphabetical order is adopted, when there is more than one type of
ligand.
The order and naming of ligands are as follows: first, anions, in the following order: H-
(hydrido), o2 (oxo); OH- (hydroxo); other simple anions such as I- (iodo); Br-(bromo); Cl-
 (chloro); F-(fluoro); polyatomic anions, such as CN- (cyano); SCN-(thiocyanato); organic
anions like C5H7O2- (acetylacetonato); C4H7O2N2- (dimethylglyoximato).
Anionic ligands end in –o, e.g. CN- cyano, Cl- chloro, OH- hydroxo, etc.
Neutral ligands rarely change , but note H2O aqua, NH3 ammine, CO carbonyl (aqua is
named first).
Positive ligands end in –ium, e.g. NH2-NH3+ hydrazinium.
7. When there is a number already stated in the name of the ligand (e.g. ethane-1,2-diamine),
then, to avoid confusion, the ligand is placed in a bracket and the prefix bis, tris, tetrakis,
etc. used instead of di, tri, tetra, etc.
Examples:

[Cr(H2O)6]Cl3 Hexaaquachromium (III) chloride

[Ni(CO)4] Tetracarbonylnickel (0)
K2 [PtCl4] Potassium tetrachloroplatinate (II)
[Pt (NH3)4]Cl2 Tetraammineplatinium (II) chloride
[Co(NH3)5NO2]Cl2 Nitropentaamminecobalt (II) chloride
[Cu(NH3)4(H2O)2]SO4 Diaquatetraamminecopper(II) sulphate (VI)
[Co(NH2CH2CH2NH2)3]Cl3 Tris (ethane-1,2-diamine) cobalt(III) chloride

History. Werner’s Theory

o Present ideas on the shapes of coordination compounds owe their origin to the work of A.
Werner, who in 1893, suggested what proved to be the correct explanation for the structures
of the coordination compounds of tripositive cobalt and a dipositive platinum.
o Using the ammines of these metals, as examples, the evidence on which Werner’s theory
was based will be reviewed.
The Cobaltammines and other 6 coordination complexes
• In addition to hexamminecobalt (III) chloride, a number of other complex salts have been
prepared, in which ammonia is strongly bound to tripositive cobalt.
• The distinctive properties of these are summarized in the table below, together with
Werner’s formulations.
• Chemical evidence to support Werner’s formulations came, for example, from conductance
measurements on aqueous solutions which indicated what ions were present.
 • Also, from the proportion of chlorine present, as the chloride ion i.e the fraction which was
precipitated by silver nitrate.
Table. The ammines of cobalt
Compound Salt Colour No. of ions Werner’s
formulations
CoCl3.6NH3 Luteo Orange 4 [Co(NH3)6]Cl3
CoCl3.5NH3.H2O Roseo Pink 4 [Co(NH3)5H2O]Cl3
CoCl3.5NH3 Purpureo Purple 3 [Co(NH3)5Cl]Cl2
CoCl3.4NH3 Praseo Green 2 [Co(NH3)4Cl2]Cl
CoCl3.4NH3 Violeo Violet 2 [Co(NH3)4Cl2]Cl
CoCl3.3NH3 Blue-Green 0 [Co(NH3)3Cl3]

• Werner proposed that each metal had both a primary and a secondary valency or a primary
and secondary coordination sphere. In the ammines of cobalt, the primary valency (or
electrovalency) is 3 and the secondary valency is 6.
• He also suggested that the secondary valencies were directed in space about the central ion
and that for 6 coordinate cobalt, the ligands were arranged octahedrally about the metal
ion.
• Then the two compounds of empirical formula COCl3. 4NH3 were regarded as geometrical
isomers (formulae (II) and (III).
• Two isomers only are possible for an octahedral arrangement and in practice no more than
two are known.
• If the arrangement were either of the other possibilities, namely trigonal prismatic or planar
hexagonal, then three isomers would be expected.
• For example, in a plane hexagon, the chlorine atoms could be in the 1,2 or 1,3 or 1,4
positions.
• The isolation of the predicted number of isomers is indicative, but not conclusive support
for Werner’s hypothesis.
• However, another consequence of an octahedral, but not of a planar or trigonal prismatic
configuration is that optical activity is to be expected for an ion, such as tris
(ethylenediamine) cobalt (III) (abbreviated to [Co(en)3]3+ , where en = ethylenediamine.
Isomerism in complexes:
• Coordination chemistry can become complicated due to the many ways isomers can arise.
There are several different isomers of coordination complexes. These include, geometrical
isomerism, optical isomerism, ionization isomerism, ionization isomerism and linkage
isomerism.
Geometrical isomerism:
• This occurs, when coordination complexes can exist in different geometries, such as cis-
trans isomers. Square complexes of the type ML2X2 can exist as cis and trans isomers.
• Isomers of octahedral complexes that are of particular importance are the trans and cis-
isomers of ML4X2 species and their facial and meridional isomers of ML3X3 species.

X X
X X
L X L X
L L L X
M M
M M L L
L L L X
L L X
X L
L

Cis Facial Meridional

Trans

Optical isomerism:
• Optical isomers are molecules that are mirror images of each other that cannot be
superimposed.
• Since, they cannot be superimposed, they are not identical, even though all their internal
distances and angles are identical.
• These isomers also react identically, unless the reactant is also one of a pair of optical
isomers.
• Their most characteristic difference, which gives rise to the term optical is that each one
causes the plane of polarization of plane-polarised light to be rotated, but in opposite
directions.
• Two molecules that are optical isomers in this sense are called enantiomorphs.
• Their existence was first recognized amongst organic compounds, when a tetrahedral
carbon atom was bonded to four different groups, as in lactic acid.

H3C CO2H HO2C CH3

C C
H OH H OH
 • One of Werner’s accomplishments was to recognize that enantiomorphs exist for certain
types of octahedral complexes.
• He prepared and resolved these compounds and used this result to support his hypothesis,
that the coordination geometry was indeed octahedral.
• Amongst the most important enatiomorphous octahedral complexes are those that contain
two or three bidentate ligands. The enantiomorphs of a M(L-L)2X2 complex are shown
below.

Ionisation isomerism:
• Compounds that have the same empirical formula may still differ with regards to which
anions are coordinated to the metal and which are present as counterions, within the crystal
lattice.
• Such isomers yield different ions, when dissolved as illustrated by the reactions below:

[Co(NH3)4Cl2]NO2 [Co(NH3)4Cl2]+ + NO2-

[Co(NH3)4Cl(NO2)]Cl [Co(NH3)4Cl(NO2)]+ + Cl-

The two complexes [Co(NH3)4Cl2]NO2 and [Co(NH3)4Cl(NO2)]Cl are ionization isomers.

Linkage isomerism

Some ligands can bind in more than one way, and often isomeric complexes with different modes
of binding can be isolated. The oldest example, is the isomeric pair.
 2+

2+
O

(NH3)5Co N (NH3)5Co O N O

Nitrito
Nitro

Coordination Isomerism:

In compounds where both the cation and anion are complex, the distribution of ligands can vary,
giving rise to isomers. The following are examples:

Co(NH3)6][Cr(CN)6] [Cr(NH3)6][Co(CN)6]
and

BONDING IN TRANSITION METAL COMPLEXES:

• Bonding in transition metal complexes can be treated in terms of the Valence Bond
approach and the Crystal Field Theory approach. Each of these will be looked at.
VALENCE BOND APPROACH to Bonding in Complexes:
According to the Valence Bond approach, the stereochemistry of complex compounds is here
treated in terms of hybridized orbitals.
In the transition metals, with which, we are largely concerned here, the d-orbitals of the
penultimate quantum shell are near in energy to the s and p orbitals of the outermost shell and
various hybridisations are possible.
The same types of hybridization can occur in the non-transition metals, but here the d, s and p
orbitals are all of the same principal quantum number.
The idea that atoms form covalent bonds by sharing pairs of electrons was first proposed by G. N.
Lewis in 1902. It was not until 1927, however, that Walter Heitler and Fritz London showed how
the sharing of pairs of electrons holds a covalent molecule together. The Heitler-London model of
covalent bonds was the basis of the valence-bond theory. The last major step in the evolution of
this theory was the suggestion by Linus Pauling that atomic orbitals mix to form hybrid orbitals,
such as the sp, sp2, sp3, dsp3, and d2sp3 orbitals.

It is easy to apply the valence-bond theory to some coordination complexes, such as the
Co(NH3)63+ ion. We start with the electron configuration of the transition- metal ion.

Co3+: [Ar] 3d6

We then look at the valence-shell orbitals and note that the 4s and 4p orbitals are empty.

Co3+: [Ar] 3d6 4s0 4p0

Concentrating the 3d electrons in the dxy, dxz, and dyz orbitals in this subshell gives the following
electron configuration.

The 3dx2-y2, 3dz2, 4s, 4px, 4py and 4pz orbitals are then mixed to form a set of empty d2sp3 orbitals
that point toward the corners of an octahedron. Each of these orbitals can accept a pair of
nonbonding electrons from a neutral NH3 molecule to form a complex in which the cobalt atom
has a filled shell of valence electrons.
At first glance, complexes such as the Ni(NH3)62+ ion seem hard to explain with the valence-bond
theory. We start, as always, by writing the configuration of the transition-metal ion. The element
Ni has 28 (twenty eight ) electrons

Ni2+: [Ar] 3d8

This configuration creates a problem, because there are eight electrons in the 3d orbitals. Even if
we invest the energy necessary to pair the 3d electrons, we can't find two empty 3d orbitals to use
to form a set of d2sp3 hybrids.

There is a way around this problem. The five 4d orbitals on nickel are empty, so we can form a set
of empty sp3d2 hybrid orbitals by mixing the 4dx2-y2, 4dz2, 4s, 4px, 4py and 4pz orbitals. These
hybrid orbitals then accept pairs of nonbonding electrons from six ammonia molecules to form a
complex ion.

The valence-bond theory therefore formally distinguishes between "inner-shell" complexes, which
use 3d, 4s and 4p orbitals to form a set of d2sp3 hybrids, and "outer-shell" complexes, which use
4s, 4p and 4d orbitals to form sp3d2 hybrid orbitals.