Coordination Chemistry

1.0 Preliminary Comments

1.1 Historical highlights

Earliest record of coordination compound was Prussian blue,

KCN.Fe(CN)3.Fe(CN)2, which was obtained by the artist maker, Diesbach in
the 18th century. The date usually cited is the discovery of
hexaamminecobalt(III) chloride, accidentally, by Tassaert in 1798, which
marked the beginning of coordination chemistry. It took about 100 years later
before any explanation was forthcoming on how CoCl 3.6NH3 was possible.
Following this discovery subsequent work was expectedly on complexes of
ammonia.

The naming of metal complexes has gone through a number of changes,

viz:
Naming after the discoverers, e.g. Reineckes salt,
Cr(SCN)3.NH4SCN.2NH3, now formulated as NH4[Cr(SCN)4(NH3)2];
Zeises salt, PtCl2.KCl.C2H4 or K[PtCl3(C2H4)]
Naming according to colour, e.g. yellow CoCl 3.6NH3 called luteocobaltic
chloride and purple CoCl3.5NH3 called purpurecobaltic chloride.
IUPAC nomenclature, which is the acceptable modern method of
naming and will be discussed in detail in this course.

Techniques employed in characterizing coordination compounds by the

pioneer workers
Simple chemical reactions, e.g. [Co(NH3)5Br]SO4 (A) or
[Co(NH3)5SO4]Br (B) involves reacting solutions of each compound with
either BaCl2/Ba(NO3)2 solution ((A gives a white precipitate whereas B
does not) or AgNO3 solution (A does not give any precipitate but B
gives a light yellow precipitate).
Conductivity experiments to determine the number of ions present in
solution, e.g. CoCl3.6NH3 (C) and CoCl3.5NH3 (D) above in which a
known mass of each is dissolved in standard flasks and their
conductivities determined. (C) gives a 1:3 electrolyte (i.e. one cation
and three anions) whereas (D) gives a 1:2 electrolyte (one cation and
two anions).
Gravimetric analysis, e.g. (C) and (D) could be distinguished
gravimetrically by taking a known mass of each, dissolve in water, and
add excess AgNO3 solution to each. The white precipitate formed in
each case can be filtered in a dry pre-weighed crucible, washed free of
soluble impurities and dried to constant mass in an oven (at a
prescribed temperature). The crucible with the content is weighed and
the mass of AgCl precipitated in each case is calculated. From the
mass of the precipitate the mass of Cl - in each case is calculated. (C)
would give 3 moles of Cl - (3 moles of AgCl) and (D) gives 2 moles of Cl-
(2 moles of AgCl) if 1 mol dm-3 solution of each is used.
Write balanced equations for the reactions of compounds C and D with
AgNO3 described and identify the precipitates

1.2 Werner Theory

Werner proposed two valences for most elements:

Primary valence (now known as oxidation state) and secondary
valence (now known as coordination number). Every element tends
to satisfy both its primary and secondary valences.
The secondary valence is directed towards fixed positions in space
(i.e. secondary valence determines the stereochemistry of
compounds)
These constitute Werners coordination theory proposed in 1893 at the age of
26 and for which he won a Nobel Prize in 1913. His theory has remained a
guiding principle in Inorganic Chemistry and in the concept of valence.
For example, CoCl3.6NH3 has a primary valency of 3 and a secondary valency
of 6.

2 Preparation of coordination compounds

Preparation of compounds is the trade mark of every chemist. Research in

chemical industries is largely oriented toward the synthesis of new and useful
materials. The chemist is interested in preparing new compounds because it
is an invaluable way of expanding our knowledge of chemistry.

There are many routes, but related experimental methods to preparing metal
complexes. The method chosen depends upon the metal, the oxidation state
of the metal, the ligand and the electron configuration of the ion. Not all
methods can therefore be employed to the synthesis of a particular
compound. Having found a suitable method for making the compound in
good yield one needs to find a suitable way to isolate the product from its
reaction mixture.

Some of the commonly used techniques to obtain products from reaction

mixtures are:
Evaporation of the solvent to concentrate (could be under reduced
pressure usin a rotary evaporator) and the cooling in an ice-bath (or a
refrigerator). Adding a seed crystal of the desired compound (if
available, and often it is not available) or scratching the inside of the
beaker below the liquid surface helps to induce crystallization.
A slow addition of a solvent that is miscible (but less polar) with the
solvent of the reaction mixture but which does not dissolve the desired
product followed by cooling, (seeding), and scratching.
For a cationic complex an appropriate anion with which it forms an
insoluble salt can be added. A suitable cation may be added to the
reaction mixture containing an anionic complex. E.g. to precipitate
[Ni(CN)5]3- from a solution add a large trivalent cation like [Cr(en) 3]3+ to
give [Cr(en)3][Ni(CN)5].
Chromatography can be used to separate and purify complexes.

2
 Other techniques are distillation (could be under reduced pressure if
the compound decomposes before its boiling point) and sublimation
(for volatile complexes), and Soxhlet extraction (of either the complex,
if soluble in extractor solvent or of the impurity if the complex is
insoluble).

2.1 General principles of synthesis coordination compounds

There are two important variables that occur in reactions involving transition
metals:
Coordination number
Oxidation state.
Either may increase, decrease, or remain unchanged in a reaction. It is, in
practice, not possible to predict either of these variables in a reaction. This is
because ligands behave in peculiar way depending on a number of
constraints. E.g. a tetradentate ligand may behave as a bidentate ligand. It is
also possible for a ligand, which should be anionic, to coordinate neutral or as
a radical. Whether a reaction results in a change of oxidation state of the
central metal or not would depend on the mode of coordination of the resulting
complex.

In general the following classifications hold:

Addition reaction: Coordination number of an electron acceptor (the

metal/metal ion) increases.
Substitution reaction: Coordination number is unchanged.
Dissociation reaction: Coordination number decreases.
Oxidation reduction reaction: There is a change in oxidation state.
Coordination compounds are also classified according to the speed at which
they undergo substitution reaction:
Complexes that undergo substitution reaction at room temperature
spontaneously are said to be kinetically labile.
Those where substitution takes hours/days are said to be kinetically
inert.

3 General rules guiding lability/inertness

3.1 Labile complexes

Complexes with central metal atom having d electrons in the e g
orbitals, e.g. [Ga(C2O4)3]3-, d10; [Co(NH3)6]2+, d7+; [Cu(H2O)6]2+, d9;
[Ni(H2O)6]2+, d8 and [Fe(H2O)6]3+, d5.
Complexes containing less than 3 electrons in the d orbitals , e.g.
[Ti(H2O)6]3+, d1; V(phen)3]3+, d2 and [Ca(EDTA)]2+, d0+.
3.2 Inert complexes
Octahedral low-spin d4, d5 and d6 complexes, e.g. [Fe(CN)6]3-;
[Co(NH3)6]3+ and [PtCl6]2-, d6.
Octahedral d3 complexes, e.g. [Cr(H2O)6]3+, d3.
Crystal field approach helps to see the picture clearly.

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3.3 Addition reactions
Addition reactions lead to increase in coordination number, usually
accompanied by colour changes.

[ML4] + Y [ML4Y]
[ML4Y] + Y [ML4Y2]

Y is an adduct and can be the solvent molecule or another molecule, e.g.

[Cu(acac)2] + py [Cu(acac)2py]

The product may or may not be isolable but the formation of the product can
be detected because of the change in coordination number.

3.4 Substitution reactions

Majority of complexes can be prepared by substitution reactions, in a number
of cases, displacing water. However, the method employed depends on
whether the complex being substituted is labile or inert.

3.5 Preparation of labile complexes

Formation of labile complexes is virtually instantaneous upon mixing of the
reactants hence there are few practical difficulties in their preparation, but
three points must be remembered:
It is, in practice, difficult to prepare such complexes with several non-
ionic ligands bonded to the same metal atom, although anionic species
may be coordinated together with a neutral ligand.
Although it may be possible to isolate and characterize a solid complex
quite a different complex may be the predominant species in solution.
Some complex ions display incongruent solubility (arising from the
second point above), e. g. if an aqueous solution containing iron(II)
sulphate and ammonium sulphate in 1:1 ratio is allowed to crystallize
then [Fe(H2O)6]SO4.(NH4)2SO4 is formed. The iron(II) ammonium
sulphate is said to show congruent solubility. However, if solutions
containing KCl and CuCl2 at ratio 2:1 are allowed to crystallize, crystals
of KCl are obtained first and only later does the complex
K2[Cu(H2O)2Cl4] crystallize. If the complex is re-crystallized there is an
initial deposition of KCl again. The complex is said to display
incongruent solubility.

3.6 Basic principles for the preparation of metal complexes

Labile complexes are prepared in aqueous medium from hydrated salts.

Inert complexes are prepared from anhydrous complexes if non-aqueous

medium is to be used. Where only hydrated salts are available, salts have to
be dehydrated first before use. If preparation is to be done in aqueous
medium then a labile complex of a lower oxidation state is oxidized or a salt at
a higher oxidation state is reduced.
Some ions are unstable to oxygen. Complexes of such ions are prepared in
an inert atmosphere, e.g. under N2 gas.

4
Examples
Substitution reaction in aqueous solution is the most common method for
labile complexes. The method involves a reaction between a metal salt in
water and a coordinating agent.

1. Action of excess ammonia on aqueous solution of copper(II) salts:

[Cu(H2O)6]2+ + 4 NH3(l) [Cu(NH3)4]2+ + 6 H2O

or
[Cu(H2O)6]2+ + 4 NH3(aq) [Cu(H2O)2(NH3)4]2+ + 4 H2O

The instant replacement of water by ammonia at room temperature is shown

by a change in colour. Other species corresponding to stepwise substitution
of the water by NH3 exist in solution, e.g. [Cu(H2O)5(NH3)]2+,
[Cu(H2O)4(NH3)2]2+, etc.
There are many labile complexes which may be studied readily in solution but
which are very difficult to obtain in the solid state.

2. Preparation of uncharged complexes

A neutral complex is usually precipitated from either aqueous solution or
aqueous alcohol and, unless highly polymeric, may be re-crystallized from
organic solvents. For example,

[Cu(H2O)6]2+ + 2 Hacac [Cu(acac)2] + 4 H2O + 2 H3O+

For this equilibrium to be displaced to the right (i.e. in favour of the formation
of the complex) the system is usually buffered to about pH 6. Sodium actate
is commonly used.

3.7 Preparation of inert complexes

As mentioned earlier, substitution is usually slow and preparations can be
done in three ways:

1. If water is not being displaced and reaction is being done in water more
drastic experimental conditions are imposed.
For example the preparation of K3[Rh(C2O4)3] is done in boiling concentrated
aqueous solutions of K3[RhCl6] and K2C2O4 for 4 h and then evaporated until
product crystallizes from the solution.

H2O, 4 h
K3[RhCl6] + 3 K2C2O4 K3[Rh(C2O4)3] + 6 KCl
wine red 100 oC yellow

To prepare [Co(en)3]Cl3 from [CoCl(NH3)5]Cl2, the rection is carried out on a

steam bath because the reaction is slow at room temperature;

[CoCl(NH3)5]Cl2 + 3 en [Co(en)3]Cl3 + 5 NH3

5
2. If water is being displaced then the water has to be replaced first
before he correct product can be obtained.
For example, Cr(III) complexes cannot be made from aqueous solvents if
water is undesirable in the complexes (alternative routes are available).
For example potassium thiocyanate (m.p. 173 o) can be used as a solvent at
elevated temperatures above 173 o. Under this condition water is readily
displaced from [Cr(H2O)6]3+.

3+ -
180o
[Cr(H2O)6] + 6 NSC [Cr(NSC)6]3-+ 6 H2O
molten KCNS

In certain instances the salt is first dehydrated before the product can be
obtained. Dehydration can be effected by use of thionyl chloride or 2,2-
dimethoxypropane. Preparation of anhydrous complexes are best done from
organic solvents and starting with, preferably, anhydrous salts, where they are
available.

Examples
1. Consider the preparation of (NEt4)2[NiCl4] from [Ni(H2O)6]Cl2.

[Ni(H2O)6]Cl2 + 6 SOCl2 NiCl2 + 6 SO2 + 12 HCl

SOCl2
NiCl2 + 2 NEt4Cl
Reflux (NEt4)2[NiCl4]
Alternatively,

[Ni(H2O)6]Cl2 + 6 (MeO)2CMe2 NiCl2 + 6 Me2CO + 12 MeOH

NiCl2 + 2 NEt4Cl (NEt4)2[NiCl4]

2. Preparation of [Cr(en)3]Cl3 from CrCl3.6H2O

[Cr(H2O)6]Cl3 + 6 (MeO)2CMe6 CrCl3 + 6 Me2CO + 12 MeOH

CrCl3 + 3 en Cr(en)3]Cl3

3.8 Oxidation-reduction reaction in the preparation of inert complexes

Oxidation
Co(II) salts are usually used as starting materials for the preparation of Co(III)
complexes;

Charcoal
CoCl2 + 2NH4Cl + 10 NH3 + H2O2 2 [Co(NH3)6]Cl3 + 2 H2O

Charcoal acts as a catalyst. In its absence the product is mostly [Co(NH 3)5X]
complexes, X = H2O or Cl.
If it is only hydrated salts of an inert complex that is available it is best to
dehydrate the salt first before use.

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Reduction
The preparation of K3[Cr(C2O4)3] from K2Cr2O7
Here the dichromate is reduced by an aqueous solution of oxalic acid and
potassium oxalate:

K2Cr2O7 + 7 H2C2O4 + 2 K2C2O4 2 K3[Cr(C2O4)3] + 6 CO2 + 7H2O

Note that in the instances where oxidation-reduction reactions are used the
starting compounds are labile. Cr(III) complexes can also be prepared from
Cr(II). However, Cr(II) compounds are rather unstable and can only be stored
under inert atmosphere.

Thermal dissociation reactions

In certain instances a new complex can form by controlled heating of another
complex, usually with evolution of a volatile compound.
For example the preparation of anhydrous copper(II) sulphate from the
hydrated salt is done by controlled heating of the latter.

96.5o 102o 115o

CuSO4.5H2O CuSO4.4H2O CuSO4.3H2O CuSO4.H2O

220o

CuSO4
The blue hydrated copper(II) sulphate loses water stepwise until all the water
of crystallization is lost to give the off-white anhydrous salt. Controlled
heating under vacuum is therefore a viable method for making a number of
complexes.

Examples
The conversion of [Cr(en)3]Cl3 to cis-[Cr(en)2Cl2]Cl is done by controlled
heating:

[Cr(en)3]Cl3 cis-[Cr(en)3Cl2]Cl

3.9 Some methods employed in characterizing coordination

compounds

Before embarking on characterization, compounds must be ascertained to be

pure. To establish purity the following could be done:

Determine the melting point. The melting point of a pure compound is

expected to be sharp. However, a sharp melting point does not
necessarily refer to the melting point of the compound anticipated.
Where the melting point of the compound has been reported, the
melting point of the compound could be compared with the literature
value.

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 Microanalysis. The percentages of all the elements present in the
compound are determined and compared with the values calculated
theoretically.

When the purity of the compound has been established the compound could
then be characterized using some of the following techniques:

Conductivity measurement. The molar ionic conductance of a

compound (the conductance of 1 mole of ions from the compound at
infinite dilution) is determined. The contribution to the molar ionic
conductance of an ion Ix is about 60 ohm-1cm2. For ions Mm+ and Xn- in
the salt MnXm the contribution will be 60m ohm -1 (from Mm+) and 60n
ohm-1 (from Xn-). Multiplying by the number of ions of each sort and
adding leads to the conclusion that a salt M nXm will have a molar
conductivity of about 120nm ohm-1 at 20 oC .

Example: The molar conductance of CoCl3.5NH3 is 261 ohm-1 cm2, hence

120nm = 261; nm = 2;
n = 1 and m = 2; n + m = 3.
That is, the number of ions is 3, hence the structure is [Co(NH 3)5Cl]Cl2.

Generally m 120nm

Chemical reactions (already mentioned under introduction)

Infrared spectroscopy (i.r.): Normally the infrared spectrum of the
ligands and the complexes are required for meaningful comparison.
The differences between the spectra fall into four categories:
1. Band positions may change
2. Relative band intensities may change. Usually new, often weak, bands
may appear.
3. Single peaks in the free ligands may split into several, closely spaced,
bands in the complex.
4. Some peaks in the ligand may disappear while new ones, particularly
in the region due to Metal Ligand bond (below 600 cm -1 may appear.
Evidence for coordination and atoms in coordination can be established from
i.r. spectra. The mode of coordination of some anionic ligands can also be
detected.

Examples
CO32- can be monodentate or bidentate. Free CO 32- absorbs at 890 cm-1;
coordinated CO32- absorbs at ~850 cm-1 (if monodentate) and at ~830 cm -1
(if bidentate).
SCN- can be S-bonded, where (C-S) is at ~700 cm -1 or N-bonded where
(C-S) is at ~820 cm-1.
NO2- could be N-bonded [(N-O) is at ~1310 cm -1] or O-bonded [(N-O) is
at ~1065 cm-1].
Stretching frequency in metal-oxygen double bond, as in V=O occurs at
960 50 cm-1.
Metal-ligand absorptions are generally weak and occur at 600 100 cm -1
region, which may present instrumental problems. Usually any i.r.

8
 spectrometer that does not record to 200 cm -1 is of limited use in
coordination chemistry. This is the region to concentrate on for M-N, M-O,
and M-X frequencies.
Infrared spectra for coordination compounds are usually recorded
preferably in the solid (KBr or CsBr pellets). There are overlaps when run
in Nujol and one cannot go below 600 cm-1 in Nujol.

Other techniques that can be used in the characterization of coordination

compounds include:
UV-Visible spectroscopy
Photoluminescence
Magnetochemistry
Thermogravimetric analysis
Differential thermal analysis
Cyclic Voltammetry (for oxidation-reduction properties of complexes)
Mass spectrometry
Nuclear magnetic resonance spectrometry
Mssbauer Spectrometry
Optical rotatory dispersion and circular dichroism (for optically active
complexes)
X-ray diffraction (which gives the ultimate structure of the compound
unequivocally)

4. Nomenclature
The International Union of Pure and Applied Chemistry (IUPAC) system will
be discussed.

4.1 Naming ligands

Ligands can be anionic or neutral. Both anionic and neutral ligands can
be monodentate or polydentate.

4.1.1 Anionic ligands

Anionic ligands end in -o

Monodentate anionic ligands:

Ligand Name Ligand Name

Cl- Chloro O2- Oxo
Br- Bromo H- Hydrido
I- Iodo O22- Peroxo
OH- Hydroxo CH3COO- Acetato
NH2- Amido SCN-; M-SCN S-thiocyanato
NO2-; M-NO2 Nitro or thiocyanato
ONO-; M-ONO Nitrito NCS-; M-NCS N-thiocyanato
CN-; M-CN Cyano or
NC-; M-NC Isocyano isothiocyanato

Bidentate anionic ligands

9
Ligand Name
acac-; [CH3COCHCOCH3]- Acetylacetonato or Pentane-2,4-
glyox-; [HONC2H2NO]- dionato
ox2-; [C2O4]2- Glyoximato
Hdmg-, [CH3CNCNCH3]- Oxalato
Dimethylglyoximato

Polydentate ligand: EDTA4-, [(O2CCH2)2N(CH2)2N(CH2COO)2]4- whose IUPAC

name is ethylenediaminetetraacetato is one of the most commonly used
polydentate ligand. The neutral tetrabasic acid is represented as H 4EDTA.

4.1.2 Neutral ligands

Monodentate

Ligand Name Ligand Name

H2O Aqua or aquo RNH2 Alkylamine
NH3 Ammine py Pyridine
CO Carbonyl (C6H5)3P Triphenylphosphine
NO Nitrosyl

Bidentate

Lgand Name Structure

en Ethylenediamine NH2CH2CH2NH2
Bipy Bipyridine

N N
1,10-phen or phen Phenathroline

N N

4.2 Naming complexes

4.2..1 If it is a salt:
Name cation first and then the anions, like in all salts. There is a space
between the cation and the anion.
Within a complex:
Name negative ligands.
Name the neutral ligands.
Name the metal (with oxidation state, in Roman numeral, in brackets).
Where there is more than one type of ligand in a complex, name in
alphabetical order or in order of complexity where they start with the same
alphabet.
For the number of ligand (of the same type) use di-, tri-, tetra-, penta- and
hexa- for 2, 3, 4, 5, and 6 respectively.
If the ligands are multi-syllabic put the name of the ligand in parenthesis. The
numerical prefixes are changed to bis-, tris-, tetrakis-, pentakis, and hexakis-
for 2, 3, 6.

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In anionic complexes the name of the metal ends -ate. In some cases the
Latin name is used; e.g. iron becomes ferrate.

In cationic complexes the metal retains its English name.

Examples

[Cr(NH3)6](NO3)3 hexaamminechromium(III) nitrate

K2[PtCl6] potassium hexachloroplatinate(IV)
K3[Fe(ox)3].3H2O potassium trioxalatoferrate(III), trihydrate or 3-water
Na[Co(CO)4] sodium tetracarbonylcobaltate(-I)
K4(Ni(CN)4] potassium tetracyanonickelate(0)
[Co(en)2Cl2]Cl dichlorobis(ethylenediamine)cobalt(III) chloride
[Co(NO2)3(NH3)3] triamminetrinitrocobalt(III)

In a neutral complex, the ligands are named first adopting the rules above
followed by the metal.
Example
[Ni(Hdmg)2] bis(dimethylglyoximato)nickel(II)

4.2.2 Bridging complexes

Ligands that bridge two centres of coordination (polynuclear) are preceded by

the Greek letter, , which is repeated before the name of each different kind of
bridging group.

H
O
[(H2O)4Fe Fe(H2O)4](SO4)2
O
H
-dihyroxobis[tetraaquairon(III)] sulphate
or tetraaquairon(III)--dihydroxotetraaquairon(III)
sulphate
H
N
[(en)2Co
Co(en)2]Cl4
O
H
bis(ethylenediamine)--imido-m-hydroxo-bis(ethylenediamine)cobalt(III) chloride
or hydroxo--imidobis[bis(ethylenediamine)cobalt(III)] chloride

11
 H
N
[(NH3)4Co Co(NH3)4] (NO3)4
N
O2

-amido--nitrobis[tetraamminecobalt(III)] nitrate

4.2.3 Point of attachment

Whenever necessary the point of attachment of a ligand is designated by

placing the symbol (in italics) of the element attached after the name of the
group is separated by hyphen.

(NH3)3[Cr(NCS)6] ammonium hexathiocyanato-N chromate(III) or

hexaisothiocynatochromate(III)
(NH3)2[Pt(SCN)6] ammonium hexathiocyanato-S-platinate(IV)

4.2.4 Naming geometric isomers

Geometric isomers are generally named by the use of the terms cis to
designate adjacent (90o apart) positions and trans for the opposite (180o
apart) positions. It is occasionally necessary to use a number system to
designate the position of each ligand. For square-planar complexes, groups
1-3 and 2-4 are in trans positions. Note that only two of the trans positions
need be numbered in the name of the second complex below. This is
because in a square-planar complex the other two ligands must then be in
trans positions. Since positions 2 and 4 are equivalent these numbers need
not be mentioned.

4 M 2

3
Number system in square-planar complexes
-
Cl NH3

NH3 Pt NH3 Cl Pt NO2

NO2 Br

trans-diamminechloronitroplatinum(II) 1-ammine-3-bromochloronitroplatinum(II) ion

12
The number system for octahedral complexes has the trans positions
numbered 1-6, 2-4, and 3-5.
1
2
5 M 3

+ 4
6
NH3 NH3
Br Br

NH3 Rh py Pt NO2
Br

NH3 Cl
NH3 I
1-ammine-2-bromo-4-chloro-6-iodonitro(pyridine)
cis-tetraamminedibromorhodium(III) ion platinum(IV)
or trans-ammineiodo-trans-bromochloronitro(pyridine)
platinum(IV)
4.2.5 Naming optical isomers

If a solution rotates plane-polarised yellow light (the Na D line) to the right, the
solute is designated a (+) isomer; if to the left, a (-) isomer.

(+) K3[Ir(C2O4)3] potassium (+)trioxalatoiridate(III)

(-) [Cr(en)3]Cl3 (-)tris(ethylenediamine)chromium(III) chloride

5 Isomerism in metal complexes

Isomerism can be divided into two broad divisions: structural isomerism and
stereoisomerism.
Structural isomerism: Ionization isomerism, hydration isomerism, coordination
isomerism, linkage isomerism, ligand isomerism, and polymerization
isomerism. Stereoisomerism: Geometric isomerism, conformational
isomerism, and optical isomerism.

5.1 Structural isomerism

5.1.1 Structural isomerism: ionization isomerism
Ionization isomerism results from the interchange of negative ligand within the
first coordination sphere of a complex that has an anion outside the
coordination sphere. Such isomers yield different ions in solution.
Examples:
[Co(NH3)4ClNO2]I and [Co(NH3)4ICl]NO2: When both are dissolved in water the
first gives a complex as cation and I - as anion whereas the second gives a
complex as cation and NO2- as anion. Other examples are [Co(NCS) 2(en)2]Cl
and [Co(NCS)Cl(en)2]NCS; Pt(NH3)3Br]NO2 and [Pt(NH3)3NO2]Br. The
isomers can be readily distinguished by appropriate qualitative analysis.
[Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br: These can also be distinguished by
appropriate qualitative analysis.

Develop qualitative analysis schemes to distinguish between each pair

of the compounds above.

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5.1.2 Structural isomerism: hydration isomerism/solvate isomerism
Hydration isomerism results from the interchange of H2O and another ligand
between the first coordination sphere and the ligand outside. Here H 2O can
be a ligand or water of crystallization.
Most common example is CrCl3.6H2O, which can give three possible isomers,
distinguishable by their colours:
[Cr(H2O)6]Cl3 Violet
[Cr(H2O)5Cl]Cl2.H2O Blue green
[Cr(H2O)4Cl2]Cl.2H2O Dark green
Other examples are [CoCl(en)2H2O]Cl2 and [CoCl2(en)2]Cl.H2O;
[CrCl2(py)2(H2O)2]Cl and [CrCl3(py)2H2O].H2O.
The isomers can be distinguished by quantitative precipitation of free chloride
using silver nitrate.

Describe how you would carry out the quantitative precipitation of free
chlorides in the isomers in 5.2. Write appropriate equations and show
how you would use your results to distinguish the isomers.

5.1.3 Structural isomerism: coordination isomerism

Coordination isomerism occurs in salts in which both cation and anion are
complex ions. Isomerism arises from interchange of ligands between the two
complex ions.
Examples:
[Co(NH3)6][Cr(ox)3] and [Cr(NH3)6][Co(ox)3]
[PtII(NH3)4][PtIVCl6] and [PtIV(NH3)4Cl2][PtII(NH3)4]
[Co(NH3)6][Cr(CN)6] and [Cr(NH3)6][Co(CN)6]
[Co(NH3)6][Co(NO2)6] and [Co(NH3)4(NO2)2][Co(NH3)2(NO2)4]

5.1.4 Structural isomerism: linkage isomerism

Linkage isomerism occurs when one or more of the ligands can coordinate to
the metal ion in more than one way. Linkages with two or more possible sites
of attachment to a metal are known as ambidentate ligands. In principle they
include NO2-, SCN-, CN-, S2O32-, CO, CONH2, CS(NH2)2, and (CH3)2SO but
only the first four have been shown to form linkage isomers.

Examples
[Co(NH3)5NO2]2+ and [Co(NH3)5ONO)]2+ are isomers . In the first one NO 2-
bonds to Co by N (a nitro complex) whereas in the second it bonds by O (a
nitrito complex). The complexes can be distinguished by using IR
spectroscopy. For the O-bonded ligand, characteristic absorption bands at
1065 and 1470 cm-1 are observed whereas corresponding bands for the N-
bonded ligand are at 1310 and 1430 cm -1. The above complexes can be
written as [Co(NH3)5(NO2-N)]2+ and [Co(NH3)5(NO2-O)]2+ respectively.
[Co(NH3)5SCN]2+ has two isomers, [Co(NH3)5SCN-S]2+ and [Co(NH3)5SCN-
N]2+, where SCN- bonds via S and N respectively. Other examples can be
found in complexes of CN- where the ligand can bond by C (cyno complexes)
or N (isocyano complexes).

14
Other examples: [dipyPd(SCN)2] and [dipyPd(NCS)2]; [Mn(CO)5SCN] and
[Mn(CO)5NCS]. All linkage isomers can be readily identified by IR
spectroscopy.
e.g. M-N=C=S has a characteristic band at 780 860 cm -1 whereas in M-S-
CN it occurs at 690 720 cm-1.

5.1.5 Structural isomerism: polymerization isomerism

Polymerization isomerism refers to complexes, which have the same
empirical formulae but different molecular masses.
Examples:
[PtCl2(NH3)2] and [Pt(NH3)4][PtCl4] and [Co(NH3)3(NO2)3] and [Co(NH3)6]
[Co(NO2)6]

5.1.6 Structural isomerism: Ligand isomerism

Ligand isomerism is due to isomerism in the organic compounds that
constitute the ligands.
Since many ligands are organic compounds and the latter have a large
number of possibilities for isomerism, the resulting complexes can show
isomerism from this source.
Examples of isomeric ligands are 1, 2-diaminopropane (pn) and 1,3-
diaminopropane (tn) or o-, m- and p-toluidine (CH3C6H4NH2). When these
compounds are used as ligands the resulting complexes are also isomeric.
e.g. [Co(pn)3 and [Co(tn)3 are isomers.

5.2 Stereoisomerism
5.2.1 Stereoisomerism: geometrical isomerism
Geometrical isomerism occurs when a metal complex of the same formula
and same basic geometry has a different arrangement of ligands. This occurs
in 4-coordinate square-planar and 6-coordinate octahedral complexes.

5.2.2 Geometric isomerism in square planar complexes

cis and trans isomerism occurs when ligands are arranged adjacent (90 o) and
opposite (180o) respectively. Common geometric isomers are found in
complexes of the type MA2B2. They are more common in Pt and Pd
complexes. Only two isomers are known in square-planar complexes of this
type. If the compound is tetrahedral only one isomer is possible..
A second type is of the form MABCD. Three square-planar complexes of this
type is possible. If it is tetrahedral, then only one isomer (which is also
potentially optically active, but not resolvable) is possible. The first type is
illustrated below:

15
 Cl Cl Cl

NH3 Pt NH3 Pt NH3 NH3 Pt NH3

NH3

Cl Cl
Cl

The trans-isomer is Asymmetric stretch Symmetric stretch

non-polar IR active IR inactive

Cl Cl Cl

NH3 Pt Cl NH3 Pt Cl NH3 Pt Cl

NH3 NH3 NH3

The cis-isomer is Asymmetric stretch Symmetric stretch

polar IR active IR active

The cis- and trans-isomers of [Pt(NH3)2Cl2] can be distinguished by IR

spectroscopy. An IR active vibration leads to a change in molecular dipole
moment.

The three isomers of the second type are given below.

A A A

D M B D M C C M B

C B D

5.2.3 Geometric isomerism in octahedral complexes

Two types of geometric isomerism are recognized in octahedral complexes:
the simple types, which exist in complexes of the type MA 2B4, in which A may
be adjacent to each other or opposite and the second for complexes of the
type MA3B2

MA2B4 type

An example is [Co(NH3)4Cl2]+

16
 Cl Cl
Cl NH3 NH3 NH3
Co Co
NH3 NH3 NH3 NH3
NH3 Cl
cis-isomer trans-isomer

MA3B3 type

Two types are possible: (1) here the ligands of one type forms an equilateral
triangle on one of the faces (the facial isomer, abbreviated as fac) and (2) the
ligands span three positions such that two are opposite, or trans, to each
other (the meridional isomer, abbreviated as mer). The following complexes
can display the fac-mer isomerism: [Ru(H2O)3Cl3]; [Pt(NH3)3Br3]+; [Pt(NH3)3I3];
[Ir(H2O)3Cl3]; [Rh(CH3CN)3Cl3]; [Co(NH3)3(NO2)3]; and [M(CO)3PR3], (M = Cr,
Mo, W).

Cl OH2
H2O Cl H2O Cl
Ru Ru
H2O Cl Cl Cl
H2O H2O
mer-isomer
fac-isomer

5.2.4 Stereoisomerism: conformational isomerism

Conformational isomerism occurs if a metal complex can exist in two totally
different geometric forms. For example, [NiCl 2(Ph2PCH2Ph)2] can exist as
square-planar in the solid state and tetrahedral in solution.

Cl Cl

Ni
Ni
Cl P
P P = PH2PCH2Ph
Cl
P
Square-planar Tetrahedral

17
Properties of geometric isomers:
One isomer is usually stable in solid. In solution it often isomerizes to a
mixture or the other isomer. For example, green trans-[Co(en)2Cl2]+
isomerizes to a mixture of cis and trans. The purple cis-isomer also
isomerises to cis and trans-isomers.
Isomers usually have different colours.
Their chemical properties are usually different; for example they react
at different rates.

5.2.5 Stereoisomerism: optical isomerism

Optical isomerism is concerned with chirality.
A molecule is chiral if it possesses a non-superimposable mirror image.
Octahedral complexes, like [Co(acac) 3], which has three bidentate chelating
ligands also possesses non-superimposable mirror images. Chiral molecules
(enantiomorphs) rotate plane polarized light in opposite directions. This
property is known as optical activity and the two mirror images are known as
optical isomers or enantiomers.
Enantiomers rotate plane polarized light to equal extents in opposite
directions, the dextrorotatory (d or +) enantiomorphs to the right and the
laevorotatory (l or -) to the left at a particular wavelength. The observation of
optical activity depends upon the chemical properties of the chiral molecules;
if the two enantiomorphs interconvert rapidly to give an equilibrium mixture
containing equal amounts of the two forms, there will not be any overall
rotation. A mixture of equal amounts of enantiomorphs is called a racemic
mixture.
A polarimeter is used to measure the rotation, , of an enantiomorph. The
amount of rotation depends on the wavelength of the light, temperature, and
the concentration of the compound. The specific rotation, [], for a chiral
compound in solution is given by:

[] =
cxl
where = observed rotation, l = path length of solution in the polarimeter (in
dm) and c = concentration (in g cm-1). Light of a single frequency is used for
specific rotation measurements and a common choice is sodium D-line in the
emission spectrum of atomic sodium; the specific rotation at this wavelength
is denoted as []D. The importance of chirality has been found in the dramatic
differences in the activities of different enantiomers of chiral drugs.

Read: E Thall (1996) Journal of Chemical Education, Vol. 73, p.481 When
drug molecules look in the mirror.

5.3 Nomenclature of chiral molecules

Nomenclature of chiral molecule is complicated.

In terms of the sign of the rotation of plane-polarized light:
- the rotation is denoted (+) or d for dextrorotatory and (-) or l for
laevorotatory
- the sign and magnitude of rotation could be incorporated ; (-)589 or (-)D
(where D is sodium D-line at a wavelength of 589 nm)

18
This method of naming defined in terms of an observable (the rotation) does
not bear any direct relationship with the absolute configuration of the
molecule.
IUPAC recommended and system

5.3.1 Definitions and notation of chiral complexes

Enantiomers are a pair of stereoisomers that are non-superimposable mirror

images.
Diastereomers are stereoisomers that are not an enantiomeric pairs.
(+) and (-)prefixes: the specific rotation of enantiomers is equal and opposite.
Enantiomers are distinguished by the sign of []D. Two enantiomers of a
compound A with []D values of +12 and -12 are denoted as (+)-A and (-)-A.
d and l prefixes: sometimes (+) and (-) are denoted by dextro- and laevo-
for right and left rotations respectively.
The +/- or d/l notation, as mentioned above, has nothing to do with the
absolute configuration of an enantiomer (the arrangement of the substituents
or ligands). The following prefixes are used for describing absolute
configuration.
R and S prefixes: this convention is used for labeling chiral carbon atoms
(tetrahedral with four different groups attached) and is based on the Cahn-
Ingold-Prelog notation.
The four groups attached to the chiral carbon atom are prioritized according to
the atomic number of the attached atoms, highest priority being assigned to
highest atomic number, and the molecule then viewed down the C-X vector,
where X has the lowest priority. The R- and S-labels for the enantiomers refer
to a clockwise (rectus) and anticlockwise (sinister) sequence of the
prioritized atoms, working from high to low. Example: CHClBrI, view down the
C-H bond:

1
1
I I

H H
C C

Cl Br
Br Cl
3 2 3
2

R S

This notation is used for chiral organic ligands, and also for tetrahedral
complexes.

and prefixes: The enantiomers of octahedral complexes containing three

equivalent bidentate ligands (tris-chelate complexes) are among those which
are distinguished using (delta) and (lambda) prefixes. The octahedron is
viewed down a 3-fold axis, and the chelates then define either a right- or a

19
left-handed helix. The enantiomer with right-handedness is labeled , and
that with left-handedness is .

Depending on the metal ion and the number and nature of chelate rings
enantiomers can be separated.

5.3.2 Rules for optical activity

An optically active compound must not have:
A centre of inversion
A plane of symmetry
An improper axis S
The mirror image must not be superimposable.

Examples of stereoisomers

[Co(en)2Cl2] can exist as cis- and trans-isomers. The cis isomer is potentially
optically active because its mirror image is not superimposable.

N N
N Cl
Co Cl N
Co
N Cl
Cl N
N N

cis-[Co(en)2Cl2]

But the trans-isomer has a plane of symmetry and a centre of inversion. It is

therefore not optically active.

20
 Cl

N N

Co

N N

Cl
trans-[Co(en)2Cl2]

The first compound to be resolved was cis-[Co(en)2(NH3)Cl]2+. It was resolved

with (+)bromo--camphor sulphate. In the solid state, the enantiomorphs are
stable. However, they often racemize in solution and therefore may not be
possible to isolate isomers even if you know they exist.
The best complexes to isolate and keep in solution are those where
M is inert (undergoes slow substitution); e.g. Co III (d6) and CrIII (d3)
complexes. For example [Co(en) 3]Cl3 is potentially active and boiling for
hours will not convert one isomer to the other. On the other hand [Zn(en) 3]2+
racemizes very rapidly because Zn2+ is a d10 ion and is very labile.
Ligands are bidentate or polydentate. Such complexes are stabilized
by chelate effect. Good examples are found in EDTA complexes.
The first purely inorganic complex to be resolved into its optical isomers was
[CoL3]6+, where L+ ligand = cis-[Co(NH3)4(OH)2]+ complex. L+ chelates through
the two O-donor atoms.

6+

H
O

Co Co(NH3)4

O 3
H

5.3.3 Methods for resolution of isomers

Most common methods used for least soluble diastereoisomers
(cations and anions) only, involve reacting the diastereoisomer with an
optically active organic anion.
For example,
() C+ + optically active organic anion (+)A- (+)C+.(+)A- and (-)C+.(+)A-
Useful for diastereoisomeric salts (not mirror images).
Employing differences in solubility of the two diastereoisomeric salts
Example,

21
()[Co(en)3]3+ + (+)tartrate2- (+)[Co(en)3].(+)tartCl.5H2O precipitates but
(-)[Co(en)3].(+)tart stays in solution. This is a practical method.
The separated diastereoisomers must now be reconverted:
Example,
(-)[Co(en)3].(+)tart + NaI (-)[Co(en)3]I3 (precipitated)
(+)[Co(en)3].(+)tart + xss KI (+)[Co(en)3]I3

Other methods
Partial asymmetric synthesis
Example
()[Fe(phen)3]2+ + (+)[SbO tartrate] (-)[Fe(phen)3].(+)[SbOtart] ppt
(+) form still remains in solution.
This method only works if the metal complex has a certain amount of mobility.
The precipitate is fairly labile and on heating, the (+) form goes to (-) form,
which is insoluble.
For anions the same technique is used except that organic cations are used
as resolving agents.
A metal complex which is optically active can itself be used as a
resolving agent for other metal complexes.

Examples,
Using (+)[Co(en)2(NO2)2]+ can be used to resolve [Co(en(ox)2]- with 100% yield
and [Co(edta)]-. Once resolved these metal complexes can be used to
resolve optically active metal cations.

5.3.4 Resolving neutral metal complexes

The complex can be adsorbed on an optically active column like quartz, (+)
lactose, or starch.

Example,
[Co(acac)3]0 on (+)lactose can be eluted with C 6H6 or hexane. One isomer is
preferentially adsorbed and one is eluted.

6 Stereochemistry

Stereochemistry is that branch of chemistry that concerns with the structures

of compounds. Inorganic stereochemistry deals with central atoms having
coordination numbers from two to twelve.

6.1 Coordination number 2

Coordination number 2 is confined to complexes of Cu I, AgI, AuI, and HgI. The
complexes are all linear. Examples include ammine complex of Ag I,
[NH3 Ag NH3]+, and cyano complex of AgI, [NC Ag CN]-. These
ions have d10 configuration. Other examples are [AgCl 2]-, [HgCl2], [AuCl2]- and
Au(CN)2-.

6.2 Coordination number 3

This is rather rare among metal complexes. Many complexes which appear
to be 3-coordinate as judged by their stoichiometry are found upon

22
examination to have higher coordination numbers. For examples, Cs[CuCl 3]
has an infinite chains Cl-CuCl 2-Cl-, a coordination number of 4; K[CuCl 3] has
an infinite double chains of Cl4-Cu2Cl2-Cl4, a coordination number of 6, having
a distorted octahedral structure; and K[Cu(CN) 2] has a chain [-CN-Cu(CN)-
CN-Cu(CN)-CN-) and is an example of true 3-coordination.
Four other examples of truly 3-coordinate complexes are the
triiodomercurate(II) anion, HgI3-, bis(thiourea)copper(I) chloride, [Cu(tu)2]Cl,
tris(trimethylphosphinesulphidecopper(I) perchlorate, [Cu(SPMe 3)3]+ClO4- and
tris(triphenylphosphine)platinum(0), [{(Ph)3P}3Pt]0. All the examples feature
ligands with bulky groups.

6.4 Coordination number 4

This coordination number is very common. The structures formed with this
coordination number can be divided into two: tetrahedral and square planar.
There are, however, intermediate structures and distortions.

6.5 Tetrahedral complexes

Tetrahedral structures are not stabilized by large CFSE (see later). The
structure is favoured by large ligands like Cl -, Br-, I- and small metal ions of
three types:

Those with a noble gas configuration ns2np6 such as Be2+, MnVII (e.g.
MnO4-)
Those with a pseudo-noble gas configuration ns 2np6(n-1)d10, such as
CuI, ZnII GaIII and Ni0.
Those transition metal ions, which do not strongly favour other
structures by virtue of the CFSE such as CoII, d7.
Specific examples for transition metal ions are MnO 4-, Ni(CO)4 and [Cu(py)4]+.
Tetrahedral complexes do not exhibit geometric isomerism, although they are
potentially optically active just like tetrahedral carbon.
Example: bis(benzoylacetonato)beryllium.

6.6 Square planar complexes

They are formed by very few metal ions. The best known are d 8 species such
as Ni2+, Pd2+, Pt2+, and Au3+. There are a few complexes of Co2+ (d7) with
bidentate ligands that are square planar, but otherwise such complexes are
rather scarce. Chlorophyll and other bio-complexes are important exceptions
to this rule where the geometry is dictated by the rigid porphyrin structure.
Square planar structure is favoured by non-bulky, strong field ligands with
sufficiently good -bonders to compensate for the energy lost through 4-
rather than 6-coordination. For example [Ni(CN) 4]2- is square planar whereas
Ni2+ forms octahedral complexes with H2O and NH3, and tetrahedral
complexes with Cl-, Br- and I-. For the heavier d8 metals steric requirements
are relaxed and the effective field strength of all ligands is increased. Under
such conditions [PdCl4]2-, [PtCl4]2-+ and [AuCl4]- are square planar.

Account for why Pd2+ and Pt2+ have stronger tendency to form square
planar complexes than Ni2+.

23
There is only a small difference in the energy of square planar and tetrahedral
complexes. Both structures can therefore inter-convert easily. A number of
Ni2+ complexes do inter-convert readily.
In the M2[CuX4] series of complexes of CuII, variation of MI and X gives
complex anions with stereochemistries ranging from square planar (e.g.
(NH4)2 [CuCl4]) to almost tetrahedral (e.g. Cs2[CuBr4].
Square planar complexes, of the formula [MA 2B2], exhibit cis-trans isomerism
(see next chapter). If such complexes are neutral molecules, they may be
readily distinguished by the presence of a dipole moment in the cis isomer but
none in the trans isomer.

6.7 Coordination number 5

The structures of 5-coordinate complexes lie between two limiting geometries:
trigonal bipyramidal and square pyramidal. These limiting structures are not
markedly different. The conversion of one structure into other requires a
relatively slight distortion.

Trigonal bipyramidal Square pyramidal

Examples: [CdCl5]3- is almost an ideal trigonal bipyramidal; [NiCl 5]3- is almost

an ideal square pyramidal.

6.8 Coordination number 6

This is the commonest and most important coordination number for transition
metal complexes. The geometry usually corresponds to six coordinated
atoms at the corners of an octahedron or a distorted octahedron.

A regular geometry
The octahedral geometry is often subjected to tetragonal distortion leading to
elongation or contraction of the axial bonds. Complexes of the type [MA 6] can
have regular geometry whereas complexes of the types [MA 5B], [MA4B2], etc
cannot have regular octahedral geometry because not all the bonds will have
the same length.

24
7 BONDING

7.1 Valence Bond Theory (VBT)

Valence bond theory assumes that bonding in coordination compounds is
solely covalent. The formation of coordinate compounds is described by the
hypothetical sequence:
Removal of electrons from the metal to give the appropriate cation.
Hybridization of those atomic orbitals which will provide a set of
equivalent hybrid orbitals directed towards the ligands.
Where necessary, rearrangement of the metals electrons in order
to ensure that the hybrid orbitals are empty.
Formation of covalent bonds by overlap of the hybrid orbitals with the
ligand orbitals containing the lone pair of electrons.
The common types of hybrid orbitals are given below:

Coordination No. Atomic orbitals Hybrid orbitals Geometry

2 spx sp Linear
3 spxpy sp2 Trigonal planar
3
4 spxpypz sp Tetrahedral
5 spxpydx2-y2 sp2d or dsp2 Square planar
2 2 2 3 2 2 3
6 spxpypzdx -y dz sp d or d sp Octahedral
[Hybridization is mixing of orbitals to get hybrid orbitals. Hybridization is not a
phenomenon, but a mathematical manipulation. Hybrid orbitals have no
physical existence in reality]

Examples
Consider CoII complexes in 4- and 6- coordinate complexes:

3d7 4s2 4p0 4d0

Co

Co2+

3
sp XX XX XX XX

3
sp hybridization- tetrahedaral

25
dsp2 *
XX XX XX XX

dsp2 hybridization- square planar

3 2
sp d XX XX XX XX XX XX

sp3d2 hybridization - octahedral

*
d2sp3 XX XX XX XX XX XX ?

d2sp3 hybridization - octahedral

XX Lone pairs of electrons from the ligand.

*
Rearranged electrons to create empty hybrid orbitals.

? The remaining electron from the CoII ion promoted to an unknown orbital.

Note: Two types of octahedral complexes are apparent: one which uses only
3d orbitals and the other which makes use of 4d orbitals for bonding. These
have been described as covalent or inner orbital and ionic or outer
orbital respectively. In the inner orbital case note the promotion of a single
electron to an unspecified outer orbital. This is in agreement with the case
with which Co2+ complexes are oxidized to Co3+.
Secondly the two forms of 6-coordinate and 4-coordinate complexes differ in
the number of unpaired, non-bonding electrons present. Since the magnetic
moments of complexes are dependent on the number of unpaired electrons,
magnetic moments can provide useful indications of structure and bond type.

Shortcomings of the valence bond theory

Other aspects of magnetic behaviours, such as variation of magnetic
moment with temperature are not explained by VBT.
Does not explain origin of colour in transition metal compounds. This is
a major shortcoming.
Does not explain why some ligands give rise to high-spin and some to
low-spin complexes.
Cannot distinguish two complexes with same number of unpaired
electrons but with different structures.

Examples
1. Discuss bonding in [Co(NH3)6]Cl3 and [CoF6]3- which are
diamagnetic and paramagnetic respectively.

26
 3d 4s 4p 4d

Co

3+
Co

[Co(NH3)6] XX XX XX XX XX XX

2 3
d sp hybridization; inner orbital octahedral complex; XX = NH3;
lone pair on N

Note that all electrons are paired, hence the complex is diamagnetic.

3d 4s 4p 4d

[CoF6]3- XX XX XX XX XX XX

3 2 -
sp d hybridization; outer orbital octahedral complex; XX = F

Note 4 unpaired electrons, paramagnetic. Magnetic moments can

therefore be used to distinguish between the two complexes.

2. Consider [Fe(H2O)6]3+ with 5 unpaired electrons and Fe(CN)6]3- with one

unpaired electron. Use the valence bond theory to explain these
observations.

3. There are three groups of complexes of Ni 2+; one group is diamagnetic

and two are paramagnetic. By considering 4-coordinate and 6-coordinate
complexes, account for the three groups of complexes.

7.2 Crystal Field Theory

7.2.1 Octahedral complexes

Crystal field theory (CFT) assumes that bonding in coordination compounds is
electrostatic (i.e. ionic). The d-orbitals fall into two groups: those whose
orbitals point along the axes (d x2-y2 and dz2) and those whose orbitals point
between axes (dxy, dyz, dxz). The shapes of the d-orbitals are given (see page
25).
In gaseous metal ion, the 5 orbitals are degenerate (i.e. of the same energy).
If a spherically symmetric field of negative charges is placed around the metal
ion, the energy of all the orbitals will be raised equally. This is as a result of
the repulsion between the negative field and the electrons of the orbitals.
When the field results from the influence of real ligands the symmetry must be
less than symmetrical because of the finite number (usually 4 or 6) of ligands
involved. When, for example, six ligands approach to form an octahedral

27
complex, there are two types of d-orbitals, the d x2-y2 and dz2, which have lobes
point along the x-, y-, and z- axes and d xy, dyz, and dxz whose lobes point
between axes. If 6 ligands are imagined to approach the cation along x-, y-,
and z- axes until they reach their final equilibrium positions then as they
approach the electrons in the metal d-orbitals will be repelled, i.e. the energy
of the d-orbitals will be increased, but not equally.
eg

Energy 6Dq 3
/5 o
o
Baricentre
=10Dq
-4Dq 2
- /5 o

t2g

Free ion Average energy of d-orbitals Splitting of d-orbital

(gaseous state) under spherically symmetric energies in
field octahedral crystal
field

The dx2- y2 and dz2 orbitals, which point directly towards the ligands will suffer
greater repulsion (i.e. higher energy) than those orbitals which point between
axes. The energies of the d-orbitals split into two sets: two axial and three
non-axial. The axial orbitals are referred to as e g while the non-axial are t2g.
Thus the eg set increases in energy while the t 2g set decreases in energy.
Their separation is given the symbol o or 10Dq and referred to as crystal field
splitting energy (for octahedral field). The energy level splitting in an
octahedral environment is given at page 26.

The separation between eg and t2g is very important because it introduces the
possibility of re-arranging the metal d-electrons. The Hunds rule still holds in
the sense that d-electrons still tend to remain unpaired until each orbital is
singly occupied before pairing can occur. However, electrons would tend to
occupy the orbitals of lower energy before the e g orbitals are filled, particularly
if the separation energy is large.

28
 eg

Energy 6Dq
3
/5 o
o
Baricentre
=10Dq
-4Dq 2
- /5 o

t2g

Free ion Average energy of d-orbitals Splitting of d-orbital

(gaseous state) under spherically symmetric energies in
field octahedral crystal
field

For d1 to d3 the electrons go singly into the t 2g orbitals; however, for d4, d5, d6,
and d7 two options are open, depending on the magnitude of o.
If o is large, i.e. the crystal field is strong the electrons are forced to
pair in the lower t2g set and the configuration is known as spin-paired
or low-spin.
If o is small, i.e. the crystal field is weak, the maximum number of
electrons remain unpaired and the configuration is known as spin-free
or high-spin.

This is summarized below:

d1 4
d2 d3 d d5

high
spin

low
spin

29
 d6 d9
d7 d8

high
spin

low
spin

9
Note that both low- and high- spin for d are the same

These arrangements correspond to the outer orbital and inner orbital types
of VBT:

Outer orbital High spin

Inner orbital Low spin

Thus the vacant orbital created to allow for vacant d-orbitals required for
hybridization (i.e. d2sp3) in VBT is equivalent to the empty e g orbital in low-spin
configuration in CFT.

For example, Co2+ octahedral complex in CFT would generate two

configurations:

eg

eg

o
o

t2g

t2g

Co2+ d7 high spin VBT outer orbital Co2+ d7 low spin VBT inner
orbital

30
Also note that the electron promoted to unknown orbital in VBT is actually in
the eg level in CFT and that o for high-spin complexes is smaller than o for
low-spin.

Other examples:
Use the crystal field theory to account for
(a) [Fe(H2O)6]3+ having 5 unpaired electrons whereas [Fe(CN) 6]3- has one
unpaired electron.

(b) [Co(NH3)6]3+ is diamagnetic whereas [CoF6]3- is paramagnetic.

7.2.2 Formation of tetrahedral complexes

Bonding in tetrahedral complexes occurs essentially the same way as in

octahedral complexes except that electrons approaching between axis (now
t2) will be more strongly repelled than those along axis (now e). The d-orbital
splitting is thus an inverted form of the octahedral.

t2

Energy 2
/5 t
Baricentre t
3
- /5 t

The separation energy between e and t 2 levels is t. Both o and t are called
crystal field splitting energies for octahedral and tetrahedral geometries
respectively. For the same metal, at the same oxidation state, and the same
ligands, t -4/9o.
The occurrence of high-spin and low-spin configurations for d 3, d4, d5 and d6
ions is also possible in principle but rather rare to have low-spin tetrahedral
complexes because of the small crystal field splitting energy involved.

Reasons why t is smaller than o

Four ligands are involved in tetrahedral complexes as against six in

octahedral. Larger crystal field is therefore expected for six ligands
than for four.
The ligands in tetrahedral complexes are less efficiently directed
(between axes) than they are in octahedral (along axes). The ligands
are therefore not aimed at any of the orbitals but exert a somewhat
larger influence on the t2g orbitals than the eg orbitals.

31
7.2.3 Formation of square-planar complexes

The square-planar geometry is usually conceived as an octahedral complex

where the axial ligands have been elongated to infinity (i.e. totally removed).
The effect of this is to reduce the energy of the d z2 orbital (which points along
the vertical axis). This would have the effect of lowering the energy of the d xz

dx2-y2

dxy

2
dz

dxz, dyz

Octahedral Square-planar

L n+

n+ n+
L
L L L L L L

L L L L L L
y x
L

Octahedral Removal of axial Square-palnar

complex ligands complex

32
and dyz orbitals of the t2g level; that is the degeneracy of the eg and t2g levels
are removed.
In the square-planar complexes of the d 7 ion, Co2+, and the d8 ions, Ni2+, Pd2+,
and Pt2+, electrons are forced to pair in the lower four orbitals, leaving the top
dx2-y2 orbital vacant. In the VBT this orbital is used for bonding. (Remember
dsp2 hybridization?)

7.3 The ligand field theory (LFT)

LFT is a modified CFT which allows the possibility of covalent bonding in
addition to electrostatic bonding in the formation of metal complexes. This
theory can account, at least qualitatively, for the crystal field splitting caused
by various ligands. Ligands like CO, CN -, phen, and NO2- which provide the
largest crystal fields, are all able to form bonds with the central metal
ion/atom. This bonding markedly increases the magnitude of o.
The magnitude of o is also strongly influenced by the oxidation state of the
metal ion and the type of d electrons present. The higher the oxidation state
of the metal ion the larger the crystal field splitting. For example, [Co(NH 3)6]3+
is diamagnetic; [CoF6]3- is paramagnetic. Ions with high charge and small
sizes can be approached more strongly by ligands than larger cations of
smaller charge.
It is also known that the greatest crystal field splitting is observed in
complexes of 5d metals and decreases from 4d to 3d. Thus o([Ir(NH3)6]3+) >
o([Rh(NH3)6]3+) > o([Co(NH3)6]3+)
The arrangement of the ligands in the order of the magnitude of their o is
known as the spectrochemical series and follows the order:

Weak field ligands Intermediate field ligands Strong field ligands

I <Br <Cl <OH <RCO2 ,F < Ox-<H2O<NH3<en<
- - - - - -
NO2-<phen<CN-CO

To account for this order the extreme assumption of pure covalency in the
VBT and pure electrostatic model of CFT must be abandoned for the
existence of both modes of bonding in metal complexes.

Values of o for selected metal complexes

Complex /cm-1 Complex /cm-1

[TiF6]3- 17 000 [Fe(ox)3]3- 14 100
[Ti(H2O)6]3+ 20 300 [Fe(CN)6]3- 35 000
[V(H2O)6]3+ 17 850 [Fe(CN)6]4- 33 800
[V(H2O)6]2+ 12 400 [CoF6]3- 13 100
[CrF6]3+ 15 000 [Co(NH3)6]3+ 22 900
[Cr(H2O)6]3+ 17 400 [Co(NH3)6]2+ 10 200
[Cr(H2O)6]2+ 14 100 [Co(en)3]3+ 24 000
[Cr(NH3)6]3+ 21 600 [Co(H2O)6]3+ 18 200
[Cr(CN)6]3- 26 600 [Co(H2O)6]2+ 9 300
[MnF6]2- 21 800 [Ni(H2O)6]2+ 8 500
[Fe(H2O)6]3+ 13 700 [Ni(NH3)6]2+ 10 800
[Fe(H2O)6]2+ 9 400 [Ni(en)3]2+ 11 500

33
Some applications of CFT

CFT provides explanations for

Colour in metal complexes;
Magnetic properties of metal complexes;
Determining the structure of complexes.

8 Colour

8.1 Origin of colour

Colour in metal complexes arises from
Transitions between metal-centred orbitals possessing d-character (d-d
transitions).
Transitions between metal- and ligand-centred MOs which transfer
charge from metal-to-ligand or ligand-to-metal (charge-transfer
transitions).

8.2 Selection rules

Electronic transitions obey the following selection rules:
Spin selection rule: S = 0
Transitions may occur from singlet to singlet, or triplet to triplet states and so
on, but a change in spin multiplicity is forbidden.
Laporte selection rule: There must be a change in parity:
allowed transitions: g u
forbidden transitions: g g and u u
This leads to the selection rule: l = 1
and thus allowed transitions are s p, p d, d f;
forbidden transitions are s s, p p, d d, f f, s d, p f, etc.

8.3 d-d transitions

d-d transitions are generally weak with 100 and broad. This is because
they are forbidden transitions. The selection rule l = 1 is broken because
for d orbital l = 2; l = 0. Colour is due to transitions between energy levels,
e.g. between t2g and eg. Absorption of a particular quantum of energy ( = h)
causes promotion of an electron from t 2g level to eg level. The value of is
such that the energy lies in the visible part of the spectrum.
At 1kJ 83.7 cm-1; o for [Ti(H2O)6]3+ 244 kJ. For this ion o = 10Dq = 20
300 cm-1. has been measured for most ligands on a wide range of metals.
Wavelengths () can be converted to wavenumbers ( ) by the equation:

1 = c

Absorption bands are described in terms of max corresponding to the

absorption Amax. The unit of is nm while that of wavenumbers is cm -1. If the
electronic spectrum is done in a solution, the extinction coefficient max of the

34
absorption must also be reported. max indicates the intensity of the absorption
and is related to Amax.

max = Amax (max in dm3 mol-1cm -1)

cxl
Generally the electronic spectra of
d1, d4, d6 and d9 complexes consist of one absorption;
d2, d3, d7, and d8 complexes consist of three absorptions;
d5 complexes consist of a series of very weak, relatively sharp
absorptions.

8.4 What does depend on?

It depends on the nature of metal within a row. In the first row
transition metals o for M2+ is 10 000 cm-1 and for M3+ 17 000 cm-1. o
therefore depends on the oxidation state of the metal ion. o for second
row transition metals is 50% larger than those of first row, i.e. increases
down a transition metal triad (3rd row TMs > 2nd row TMs > 1st row TMs.
For example: [M(NH3)6]3+, Ir > Rh > Co
41 000 34 000 23 000 cm-1

Greatly on the nature of the ligand. increases along the

spectrochemical series:I < Br < Cl < F < OH < Ox- < H2O < NH3 < en <
- - - - -

phen < NO2- < CN-

All these facts enable the colours of complexes to be predicted.
[Ti(H2O)6]3+, 490 nm; [TiCl6]3-, >490 nm; [Ti(CN)6]3-, <490 nm.

Hole formalism
d10-n configuration behaves in CF similarly to dn configuration.
8.5 Charge-transfer transition

There are two types: metal-to-ligand (ML) oxidation

or ligand-to-metal (M L) reduction, which occurs usually as s p or p
d or d p. These are allowed transitions and are therefore very intense.
[Ti(H2O)6]3+, a d1 ion, is purple whereas [Ti(H 2O)6]4+, a d0 ion, is yellow. The
purple colour in the former is due to d-d transition, whereas the yellow colour
in the latter is due to charge-transfer transition.

9 Thermodynamic effect on crystal field splitting

The separation of d-orbitals into t 2g and eg levels translates into making the t 2g
orbitals more stable and the e g orbitals less stable than the degenerate
orbitals. Consequently a t2g electron increases the stability of an octahedral
complex by 2/5o and an eg electron decreases it by 2/5o. The net effect of all
the d electrons represents the additional stability which may be thought to
accrue because the CF splits the d-orbitals. This is known as Crystal Field
Stabilization Energy, CFSE. This extra stability reflects in experimental values
of such thermodynamic quantities as hydration energies, lattice energies, and
standard reduction potentials. The most complete set of data is the hydration

35
energies of bivalent ions: the experimental values of H o lie on an irregular
double-humped curve.
If the CFSE is, in each case, subtracted from H o, the corrected values fall
very neatly on a smooth curve, passing through the points for the spherically
symmetrical d0, d5, and d10 ions. CFSE, therefore, offers a ready explanation
of the Irving-Williams order of stability, MnII < FeII < CoII < NiII < CuII > ZnII.

2900

2800

o
2700 o o
o o
o o
o
2600
o
o

2500

2400

Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn

Hydration energies corrected for CFSE

o Hydration energies of bivalent transition metal ions

9.1 Calculation of CFSE

A total crystal field stabilization energy is calculated by adding up the Dq

energies for each electron after the low-spin or high-spin configuration has
been established.

Example: Calculate the CFSE for Cr3+ and Fe3+ ions.

Draw the crystal field energy level diagrams for each and in the case of Fe 3+,
draw for both low-spin and high-spin configurations before calculating the
CFSEs.

CFSE = [6Dq (No. of electrons in the eg level)]+[-4Dq (No. of electrons in the t2g
level)]

36
 = Dq [6 (No. of electrons in the eg level)] [4 (No. of electrons in the t 2g
level)]

Cr3+, d3 ion:

+6Dq

-4Dq

CFSE = 6 Dq x 0 -4 Dq x 3 = -12 Dq

+6Dq +6Dq

-4Dq

-4Dq
Weak field

Strong field
For weak field

CFSE = 6 Dq x 2 4 Dq x 3 = 12 Dq 12 Dq = 0 Dq

For strong field

CFSE = 6 Dq x 0 4 Dq x 5 = -20 Dq

The lower the CFSE, the more stable the complex. Thus low-spin Fe 3+ is
more stable than high-spin Fe3+. Also low-spin Fe3+ ion is more stable than
Cr3+ ion.

10 Jahn - Teller distortion

A regular octahedral environment is the most stable one for a spherically

symmetrical metal ion surrounded by six donor atoms. For metal ions with
certain d electron configurations which are not spherically symmetric, the
regular octahedral configuration is not the most stable. This situation is
expressed in Jahn Teller theorem: Any non-linear molecule that is in an

37
electronically degenerate state will undergo distortion to lower the symmetry,
remove the degeneracy, and lower the energy. Jahn Teller distortion occurs
strongly in all cases where the e g level is not uniformly occupied by electron.
Much weaker distortion also occurs if the t2g level is not uniformly occupied.
In the case of eg, any odd electron can occupy either the d z2 or the dx2-y2
orbital. If, however, the complex undergoes distortion the e g level is split and
the electron can occupy the lower of the two orbitals (the d z2 orbital in the case
of tetragonal elongation, or the d x2-y2 orbital in the case of tetragonal
compression).

In tetragonal elongation the ligands on the z axis move out and therefore
interact less with those orbitals which have a z component; i.e. the d z2, dxz,
and dyz, and these orbitals attain lower energy (i.e. stabilized). Those orbitals
without a z component, i.e. d x2-y2 and dxy, will be raised a corresponding
amount.

Compression: dx2-y2 attains lower energy

dx2-y2

L L
L
a
dz2
e L
L
L
dxy
Bond length a < e

dxz, dyz
1 band

3 possible bands

Elongation: dz2 attains lower energy

38
 dz2

dx2-y2 a
L L

dxz, dyz L e L

L
Bond length a > e
dxy
1 band

3 possible bands

Consequently an ion which is susceptible to Jahn Teller distortion could

produce additional bands (maximum of three altogether). Some of the
additional bands may often appear as shoulders, depending upon the
magnitude of the distortion.
Configurations d4, d7, and d9 are the most distorted. In high-spin d 4, low-spin
d7, and d9 the eg level is not evenly occupied and are therefore susceptible to
strong Jahn Teller distortion.
Uneven occupation of the t2g orbitals also results in distortion but much
weaker than in uneven occupation of e g orbitals. Thus Ti3+, d1- is less distorted
than Cu2+, d9.
Relatively weak distortions are expected for tetrahedral complexes with d 3, d4,
d8, and d9 configurations. Why?

Other evidences of Jahn Teller distortion

IR can usually detect weakening of ML bonds as a result of

distortion.
X-ray structure would reveal unusually long or short bond lengths.

11 Stability of coordination compounds

Most measurements of stability are done in aqueous solutions when the

complex in question is formed by a ligand displacing water from the aquo
complex of the metal ion. Metal complexes are formed in solution by stepwise
reaction, and equilibrium constants can be written for each step. For
example,

[Ag(H2O)x]+ [Ag(NH3)(H2O)x-1]+ + H2O k1

[Ag(NH3)(H2O)x-1]+ + NH3 [Ag(NH3)2(H2O)x-2]+ + H2O k2

39
For simplicity we can ignore the water molecules that make up the hydration
sphere of an aqueous metal ion. Moreover, the solvent water molecules
involved in the reaction are not included in the equilibrium constants, k 1 and k2
above are called stepwise-wise stability constants.

[Ag(NH3)+] [Ag(NH3)2+]
k1 = ; k2 =
[Ag+][NH3] [Ag(NH3)+][NH3]

The larger the value of the constant, the greater the concentration of the
complex species at equilibrium. A second type of equilibrium constant, ,
called an overall stability constant can be defined for the reactions above:

[Ag(NH3)+] [Ag(NH3)2+]
= ;
[Ag+][NH3] [Ag+][NH3]2

Since the ks and s describe exactly the same chemical systems, they must be
related to each other:

[Ag(NH3)2+] [Ag(NH3)2+] [Ag(NH3)+]

= .
[Ag(NH3)+]
+
[Ag ][NH3] 2 [Ag+][NH3][NH3]

[Ag(NH3)2+] [Ag(NH3)+]
= .
[Ag(NH3)+][NH3] [Ag+][NH3]
= k 2 . k1
Note that 1 = k1 and 2 = k2 . k1. By similar treatment it can be shown that
n = k1 k2 k3 ..kn.
The numerical value of stability constant describes the relative concentration
of species at equilibrium. Large stability constants indicate that the
concentration of a complex is much greater than the concentration of the
components it is made.
A complex is said to be stable if the equilibrium constants describing its
formation is large.

10.1 Factors that influence complex stability

The equilibrium constant of a reaction is a measure of heat released in the

reaction and the entropy change during the reaction.

-RT lnk = G = H TS

The larger the heat evolved in a reaction the more stable are the reaction
products. The following factors affect stabilities of complexes:

The metal ion and its charge. For example, M 3+ complexes are more
stable than M2+. Recall: Mn2+<Fe2+<Co2+<Ni2+<Cu2+>Zn2+, which is the
reverse of the order for the cation sizes.

40
 The relationship between metal and donor atoms. Class-a acceptors
or hard acids (metals in Group IA and IIA along with the inner transition
metals and the early members of the first row transition metals) form
their most stable complexes with ligands containing O, N or F donor
atoms. Class-b acceptors or soft acids (other metals form their most
stable complexes with ligands containing heavier members of N, O,
and F groups). For example, Rh, Pd, Ag, Ir, Pt, Au and Hg are class-b
acceptors. The remaining transition elements are regarded as
borderline.
The types of ligands. Bidentate ligands form more stable complexes
than monodentate ligands due to chelate effect. Chelate effect is
stabilized due to chelation. The chelate rings of 5 and 6 are more
stable. The stability of a metal chelate is greater than that of an
analogous non-chelated metal complex. For example, the stability of
[Ni(en)3]2+ is greater than that of [Ni(NH3)6]2+. The more extensive the
chelation the more stable the system.

Ligand logks Co2+ Ni2+ Cu2+ Zn2+

NH3 logk1 2.1 2.8 4.2 2.4
logk2 1.6 2.2 3.5 2.4
logk3 1.1 1.7 2.9 2.5
logk4 0.8 1.2 2.1 2.2
logk5 0.2 0.8 -0.5 -
logk6 -0.6 0.03 - -
en logk1 6.0 7.5 10.6 5.7
logk2 4.8 6.3 9.1 4.7
logk3 3.1 4.3 -1.0 1.7
trien logk1 8.1 10.7 16.0 8.9
logk2?
6-en logk1 15.8 19.3 22.4 16.2

trien = diethylenetetramine 6-en = pentaethylenehexamine

NH2 H2N

= H2NCH2CH2(NHCH2CH2)4CH2CH2NH2

NH HN

Why is Co2+<Ni2+<Cu2+>Zn2+?
Why 6 NH3, 3 en, 2 trien and one 6-en?
Why is logk1 > logk2 > logk3> ?
Why is logk6 for [Co(NH3)6]2+ negative?
Why is logk5 and logk6 negative or non-existent for [Cu(NH3)6]2+?
Why is log 6 (for NH3 complexes) < log 3 (for the en complexes) < log 1
(for 6-en complexes) in each metal?

41
For steric reasons large bulky ligands form less stable metal complexes than
do analogous smaller ligands. For example H2NCH2CH2NH2 forms more
stable complexes than (CH3)2NCH2CH2N(CH3)2.

Examples:

Complex s
[Ni(NH3)6]2+ 1 2 3 4 5 6
5 x 102 6 x 104 3 x 106 3 x 107 1.3 x 108 1.0 x 108
[Ni(en)3]2+ 1 2 3
5 x 107 1.1 x 1014 1.4 x 1018
[Ni(dien)2]2+ 1 2
6 x 1010 8 x 1018

dien = H2NCH2CH2NHCH2CH2NH2

Ref.: Basolo & Johnson, Coordination Chemistry, p. 89.

For NH3 6 s; for en 3 s; for dien 2 s. Why?

s [Ni(dien)2]2+ > [Ni(en)3]2+ > [Ni(NH3)6]2+. Why?

The successive stability constants for [Cu(H 2O)5NH3]2+, [Cu(H2O)4(NH3)]2+,

and [Cu(H2O)3(NH3)3]2+ are x, y, and z respectively. Write equations for
each step and calculate the overall formation constant for
[Cu(H2O)3(NH3)3]2+.

42
43