CH 221

Coordination and Organometallic

Chemistry

2019-2020

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 Objective
To introduce structural and mechanistic features of
metal complexes, forming the basis for a variety of
inorganic and metal-organic reactions, which are of
chemical and biological significance.

Learning Outcomes
Through this course, extended understanding of
complex bonding principles and reactivity involving
the main and transition metals, and the key role the
metal-carbon bonded systems can play in modern life,
will be imparted.
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 Course Content
1 Introduction to Coordination Chemistry
• Early ideas, double salts and metal complexes, Werner’s
theory, Types of ligands , Effective Atomic Number
(EAN), Nomenclature, Isomerism.

2 Theories of Bonding
• Valence bond theory (hybridization and coordination
numbers),
• Crystal field theory,
• Introductory treatment of molecular orbital theory
• Spectral and magnetic properties of coordination
compounds
• Applications in qualitative and quantitative analysis

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3. Reaction Mechanism in Coordination Compounds
Substitution in square planar complexes, Trans effect,
Substitution and racemization in complexes and
Electron transfer reactions.
4. Main group organometallics:
Preparations, structure, bonding, reactivity and
application of some selected s and p-block
organometallics.
5. Transition metal organometallics:
18 electron rule, types of organometallic reactions,
preparations, properties, structures and applications of
alkyl, aryl, cyclopentadienyl and carbonyl metal
complexes.
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 Coordination chemistry
(Chemistry of metal complexes)

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 Early ideas
• Much of the chemistry of transition elements is
concerned with the chemistry of coordination
compounds.

• Coordination compounds are widely present in

minerals, plants, animals and microorganisms and
play many important functions.

• Their study has contributed greatly to our

understanding of the chemical bond and of
inorganic chemistry as a whole.
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 For many years complexes were regarded as of
interest to the theoretical and inorganic chemist only,
but now they are playing vital roles in:

our understanding of biological processes e.g. in

chlorophyll, haemoglobin and vitamin B12 are
coordination compounds of Fe, Mg and Co,
respectively.

They also find extensive use in metallurgical

processes, analytical and medicinal chemistry and in
the synthesis of many organic chemicals.

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• A complex is a central metal atom or ion surrounded by
a set of ligands.

• Ligands are ions or molecules that can have an

independent existence and donate a pair of electron to
the central metal atom or ion.

• Therefore, a complex is formed when a number of ions

or molecules directly attached to the central atom
exceeds the normal covalency (oxidation state) of this
atom.

• Complexes may be neutral (no charge), cationic

(positively charged) or anionic (negatively charged).

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Examples are:
• [Ag(NH3)2]+ which is a complex because the number
of bonded groups exceeds the +1 oxidation state of
silver.
• [Co(NH3)6]3+, in which the Co3+ ion is surrounded by
six NH3 ligands.
• The complexes [Co(NO2)6]3- and [AlF6]3- are anionic.

 The term coordination compound is used to mean a

neutral complex or an ionic compound in which at
least one of the ions is a complex.
• Thus, [Ni(CO)4] and [Ni(NH3)6]Cl3 are both
coordination compounds.

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 Note:
• A complex (appropriately, ‘coordination entity’) is a
combination of a Lewis acid (the central metal
atom) with a number of Lewis bases (the ligands).

• The atom in the Lewis base (ligand) that forms the

bond to the central atom is called the donor atom,
because it donates electrons used in bond
formation.

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• The metal atom or ion, the Lewis acid, in the
complex, is the acceptor atom

• Complexes are responsible for many of the observed

properties of chemicals such as color and solubility
of salts.

E.g. most of the familiar blue copper (II) salts are

complexes containing co-ordinated water molecules.

CuSO4 + H2O (excess) [Cu(H2O)6]2+ + SO42- (aq)

White blue

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•The branch of chemistry in which coordination
compounds are studied is called the coordination
chemistry.
•Some other well-known coordination compounds are
shown in Table below.

‘Simple’ Ligand Complex

compound or
ion
BF3 NMe3 NMe3.BF3
AgCl Cl- [Ag(Cl)2]-
Cu2+ NH3 [Cu(NH3)6]2+
Al3+ F- [AlF6]3-
Ni2+ H2O [Ni(H2O)6]2+
Co3+ NO2- [Co(NO2)6]3-
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 Double salts and metal complexes

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• In a complex ion, the anion or cation concerned is
actually present as a discrete entity either in solution
or in the solid state or in both.

• In double salts, the individuality of constituent salts

is maintained (are reversibly dissociated into
constituent salts in solution).

• For instance, potash alum KAl(SO4)2.12H2O reacts

chemically as a mixture of potassium sulphate and
aluminium sulphate and does not contain or show
reactions of the [Al(SO4)2]− ion.

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•However, there is a complex ion within this double salt.

•Potash alum contains the ion [Al(H2O)6]3+ and like

aluminium sulphate it gives this ion in aqueous solution.

•A more instructive way to write the formula for potash

alum is thus K+[Al(H2O)6]3+(SO42−)2.6H2O.

•The other example is KCl.MgCl2.6H2O (carnallite).

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 Double salt
• Additional or molecular compounds formed by two
apparently saturated compounds but they lose their
identity when dissolved in solution.

• E.g Mohr’s salt, FeSO4.(NH4)2SO4.6H2O dissolves in water

to give the following ions.

• Thus, double salts are stable in solid state but break into
constituents when dissolved in water.
• What about [Ni(NH3)6]Cl2?
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 Double salt vs complex compounds
Deference Double salt complex compound
number

1 Exists only in solid state and Exists in the solid state as well
dissociates into ions in as when dissolved in water or
aqueous solution or in any any other solvent
other solvent
2 Lose their identity in solution Do not completely lose their
identity in solution
3 Have properties which are Have different properties
essentially the same as those from constituent compounds
of constituent compounds
4 Metal ions exhibit their Metal ions are surrounded by
normal valence. ligands that exceeds the
normal valence of the metal.
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 Werner’s Theory

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• Werner presented his first paper on coordination
compounds in 1891 at the age of 25 and in 1913,
received the Nobel prize for chemistry.

• The cobaltammines which attracted much of his

attention have contributed much to our
understanding of coordination chemistry.

• On the basis of conventional valencies, the formula

for simple salts CaCl2, Mg(NO3)2, CrCl3, Ba(COO)2,
PtCl2, CoCl3 are readily explainable where the
valencies are Ca = +2, Mg = +2, Cr = +3, Pt = +2, Co =
+3: Cl = -1, NO3 = -1, (COO)2 = -2.
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• The formulae of the type, for example, CrCl3.6NH3;
PtCl2.4NH3; CoCl3.6NH3; CrCl3.6H2O; failed to meet
established electrovalency requirements, and thus
posed a challenge to known bonding models.

• Some theories before him such as that of Jørgensen,

proposed the chain (“catenation”) theory in which, for
example, CoCl3.6NH3 was formulated as catenation
linkages a kin to known carbon structures, but these
proved unverifiable and unacceptable.

NH3 Cl

Co NH3 NH3 NH3 NH3 Cl

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NH3 Cl 20
 Werner’s postulates
• Two types of valencies exist for an ion, and they are
called the primary (or ionizable) valencies and
secondary (or nonionizable) valencies (now called
oxidation state and coordination number
respectively).

• The number of the secondary valencies for an ion is

fixed, e.g. six for Pt4+, Co3+, Ti3+, Fe3+; four for Pd2+,
Pt2+, Cu2+, Ni2+ ; and two for Cu+, Ag+, Au+, and Hg2+.

• The secondary valencies must be satisfied by the

anions or neutral molecules having lone electron pair
(e.g. halide, cyanide, ammonia, amines, water etc.)
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 • In a compound, the secondary valencies must be
satisfied completely.

• After these valencies are satisfied, the primary

valencies are satisfied by the anions if the complex
formed is cationic, or vice versa.

• The secondary valencies are fixed in space and

possess a definite geometric arrangement even in
solution.
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 •Thus the four secondary valencies of nickel are
tetrahedral, of Cu2+ are planar and the six secondary
valencies of Co3+ or Cr3+ are octahedral.

•Using these postulates, Werner was able to account

for the different properties of the cobalt(III) chloride
and ammonia complexes by assigning six secondary
valencies to cobalt(III).

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 Complex Common name Colour Moles of Cl- Conductivity Werner’s
Precipitated (˄M) formulation
Ohm-1cm2

CoCl3.6NH3 Luteocobaltic Yellow 3 431.6 [Co(NH3)6]3+.3Cl-

chloride

CoCl3.5NH3 purpureocobalt Purple 2 261.3 [Co(NH3)5Cl]2+.2

ic chloride Cl-

CoCl3.4NH3 praseocobaltic Green 1 - [Co(NH3)4Cl2]+.Cl

chloride -

CoCl3.4NH3 violeocobaltic violet 1 - [Co(NH3)4Cl2]+.Cl

chloride -

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 Experimental evidence

a) Ionizable chloride
• In experiments involving ionizable chlorides Werner
treated a mole of the compound with excess
aqueous AgCl or AgNO3 and noted a distinction.

• For first two complexes, three and two moles of AgCl

precipitate per mole of complex, respectively, while
for the other two, either produces only one mole of
AgCl.

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 From the facts he concluded that the non-ionizable
chlorines are covalently bonded to the cobalt.

The ionizable chlorides are just the number of free

chloride ions required to balance the charge on the
cobalt cation as a whole; hence the formulation of
the compounds.

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 b) Molar conductivity
• A further method of testing the degree of ionization
of a complex is the measurement of its electrical
conductivity in solution.

• The more ions that a complex liberates in solution,

the greater the conductivity; a complex that does
not ionize, will have negligible conductivity.

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 By measuring the molar conductivities (˄M) of some
simple salts, the relationship between the number of
ions present per molecule and the conductivity can be
established.

Thus, ˄M (Ohm−1cm2) values in water at 10−3 M are

about 120, 260 and 400 for 1:1 (e.g. NaCl), 1:2 (e.g.
BaCl2, Ca(NO3)2] and 1:3 (e.g. CeCl3), respectively.

The following table shows the molar conductivities and

the consequent formulations of some complexes.
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 Conductivities of Some Coordinated Complexes
Empirical formula Molar Formulation No. of ions
conductivity
Non-electrolytes
PtCl4.2NH3 3.5−7* [Pt(NH3)2Cl4] 0
1:1 electrolytes
NaCl 124 2
PtCl4.3NH3 94 [Pt(NH3)3Cl3]Cl 2
PtCl4.NH3.KCl 107 K[Pt(NH3)Cl5] 2
1:2 and 2:1 electrolytes
CaCl2 260 3
CoCl3.5NH3 260 [Co(NH3)5Cl]Cl2 3
CoBr3.5NH3 258 [Co(NH3)5Br]Br2 3
CrCl3.5NH3 260 [Cr(NH3)5Cl]Cl2 3
CrBr3.5NH3 280 [Cr(NH3)5Br]Br2 3
PtCl4.4NH3 229 [Pt(NH3)4Cl2]Cl2 3
PtCl4.KCl 257 K2[Pt(Cl)6] 3
1:3 and 3:1 electrolytes
LaCl3 394 4
CoCl3.6NH3 432 [Co(NH3)6]Cl3 4
CoBr3.6NH3 427 [Co(NH3)6]Br3 4
CrCl3.6NH3 442 [Cr(NH3)6]Cl3 4
PtCl4.5NH3 404 [Pt(NH3)5Cl]Cl3 4
1:4 electrolytes
PtCl4.6NH3 523 [Pt(NH3)6]Cl4 5
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 Types of ligands

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 a) Depending on the number of donor atoms

• Monodentate Ligands: have only one source of a

lone pair of electrons or one donor atom.
E.g: NH4OH, (C2H5)3N, NH3, H2O, NO, CO etc.

• Bidentate Ligands: have two sources of lone pairs

of electrons or two donor atoms

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 Polydentate ligands- these includes ligands having
more than two donor atoms attached in the molecule,
and can be called the tri, tetra, penta or hexadentates
depending upon the number of the donor atoms
present.
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 •Chelating Ligands: bidentate–polydentate ligands
which can form a straight ring structure including
the metal.

•They have several donor atoms arranged in such a

way that they can interact with one metal centre.
E.g: en, Oxalato, EDTA4-.

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• The complex having chelating Ligands is called a
chelate or chelated complex.

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 Bridging Ligands: Act as a bridge between two or
more metal centers. Important bridging ligands are:
OH-, S2-, CO32-, PO43-, NH2- etc.

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 • Ambidentate Ligands: Have two donor atoms but
their geometrical arrangement does not allow
them to bind to the same metal i.e. they cannot
form a chelate ring.

These include: CN-, CO, SCN-, NO2-

e.g: [Co(NH3)3(NO2)3], [Co(NH3)3(ONO)3]

[Co(NH3)5SCN]2+, [Co(NH3)5NCS]2+
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 Polysyllabic Ligands: the ligands whose names
include prefixes like di, tri, tetra or number etc.

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 b) Depending on the charge of the ligand

• Neutral Ligands

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Anionic Ligands: The names of negative ligands end
with -o.

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 If more than one ligand is attached then
2 = di
3 = tri
4 = tetra
5 = penta
6 = hexa

If a ligand has di, tri, tetra, in its name then use

2 = bis
3= tris
4 = tetrakis
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NOTE:
• It is not necessary that a polydentate ligand should
always use all its donor atoms for the coordination
purposes.

• Thus sulphate or nitrate ion may act as a mono or a

bidentate ligand depending on the complexes
concerned; and EDTA, a hexadentate may act as a
tetra, or pentadentate depending on the size and the
stereochemistry of the complex.

• Though OH- or NH2- act as monodentates, they can

also function as bidentates for the bridging purposes.

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