INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

COORDINATION COMPOUNDS
The formation of coordination compounds (also called complexes) is the most distinctive
aspect of transition metal chemistry. Coordination compounds are electrically neutral ionic
compounds consisting of a metal atom or ion, and one or more ligands (atoms, ions, or
molecules) that formally donate electrons to the metal. A coordination compound contains
one or more complex ions i.e. [Co(NH 3)6]Cl3 or [Co(NH3)5Br]2[Fe(CN)6], in which a small
number of molecules or ions surround a central metal atom or ion, usually of the transition
metal family. In other word, coordination compound typically consists of at least one
complex ion and counter ion(s) sufficient to give no net charge. However, some coordination
compounds such as Fe(CO)5,Ni(CO)5 etc. do not contain complex ions. For Ni(CO) 5, the
central metal is an atom, and this coordinates ligands.

The name coordination compound comes from the coordinate covalent bond, which
historically was considered to form by donation of a pair of electrons from one atom to
another. In coordination compounds the donors are usually the ligands, and the acceptors are
the metals. Coordinate covalent bonds are identical to covalent bonds formally formed by
combining one electron from each atom; only the formal electron counting distinguishes
them. Coordination compounds are also acid-base adducts, frequently called complexes or, if
charged, complex ions. A coordination compound behaves like an electrolyte in water: the
complex ion and counter ion(s) separate from each other but the complex ion behaves like a
polyatomic ion: the ligands and central metal ion remain attached.

For example
[Co(NH3)6]Cl3 [Co(NH3)6]3+ + 3Cl-
1 mole of [Co(NH3)6]Cl3 yields 1 mole of [Co(NH3)6]3+ion and 3 moles of Cl-

A typical coordination compound is [Co(NH3)6]Cl3, the complex ion (always enclosed in

square bracket) is [Co(NH3)6]3+, the six NH3 molecules bonded to the central metal ion (Co3+)
are ligands, and the three(3) Cl- ions are the counter ions. Also, the Co 3+ acts as the Lewis
acid (electron acceptor) while the six NH3 molecules act as the Lewis base (electron donor).

CENTRAL METAL ION

These are cations of the transition metals or main group metals.

NWAKIFE, C. N.
1
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

LIGANDS
A ligand is an atom, ion, or molecules that formally donate electrons to the metal. It can also
be referred to as the molecules or ions that surround the metal in a complex ion. The
interaction between a metal atom and the ligands can be thought of as Lewis acid-base
reactions. Every ligand has at least one unshared pair of valence electrons which can be used
to form bond. Examples of ligands having lone pair of electrons are as shown:

N
O -
H
H
H
H H
Cl c o
Ligands play the role of Lewis bases. On the other hand, a transition metal atom (in either it’s
neutral or positively charged state) acts as Lewis acid, accepting (and sharing) pairs of
electrons from the Lewis bases. Thus, the metal-ligand bonds are usually coordinate
covalent bonds. The atom in a ligand that is directly bonded to the metal atom or cation is
known as the donor atom. For example, nitrogen is the donor atom in the [Cu(NH 3)4]2+
complex ion.

COMPLEX ION
A complex ion is a charged species consisting of a central metal cation that is bonded to
molecules and/ or anions called ligands. Complex ions are written inside square bracket, even
though the formed species are not ions. Complex ions do not dissociate in solution but
remains as polyatomic ion. In order to maintain charge neutrality or balance charge(s) in
the coordination compound, the complex ion is associated with other ions called counter
ions.

Counter ions
Counter ions are either cations or anions that neutralize or balance the charge on the complex
ion in a coordination compound.

NWAKIFE, C. N.
2
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

STRUCTURES OF COMPLEX IONS: COORDINATION NUMBERS,

GEOMETRIES AND LIGANDS
A complex ion is described by the metal ion and the number and types of ligands attached to
it. Its structure is related to three characteristics namely:
1. Coordination number
2. Geometry, and
3. Number of donor atoms per ligands

1. COORDINATION NUMBER
Coordination number is defined as the total number of ligands or donor atoms that are
bonded directly to the central metal ion or atom in a complex ion and it is specific for a
given metal ion in a particular oxidation state and compound. Coordination number is
also known as secondary valence and it can vary from 2 to 8 depending on the size,
charge and electron configuration of the metal ion.

For example
1. [Co(NH3)6]3+
The coordination number of the Co3+ ion is 6 because six ligand atoms (N from
NH3) are bonded to it.

2. [Ag(NH3)2]+
Coordination number of Ag+ is 2

3. [Cu(NH3)4]2+
Coordination number of Cu2+ is 4

4. [Fe(CN)6]3-
Coordination number of Fe3+ is 6

The coordination number of the Pt2+ ion in many of its complexes is 4, whereas Pt4+ ion in its
complexes is 6. Copper(II) ion may have a coordination number of 2, 4, and 6 in different
complex ions.

NWAKIFE, C. N.
3
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

Exercise
Determine the coordination number of the metal ion in the following coordination
compounds:
1. [Ru(NH3)5(H2O)]Cl2
2. [Cr(NH3)6](NO3)3
3. [Fe(CO)5]
4. K4[Fe(CN)6]
5. K[Au(OH)4]

2. NUMBER OF DONOR ATOMS PER LIGANDS

Donor or litigating atom is referred to as that particular atom of the ligand molecules or
anions that actually provides the electron density to a central metal atom or ion. Ligands
have at least one lone pair of electrons and these are regarded as donor atoms. The donor
atoms often come from Group 5A(15), 6A(16), or 7A(17).

Depending on the number of donor atoms per ligands present, ligands are classified in
terms of the number of donor atoms, or “teeth,’’ that each uses to bond to the central
metal ion or atom and they are:
A. Monodentate ligands
B. Bidentate ligands
C. Polydentate ligands

A. Monodentate (Latin, “one toothed”) Ligands

H2O and NH3 are monodentate ligands with only one donor atom each.

B. Bidentate (Latin, “two teethed”) Ligands

These have two donor atoms, each of which bonds to the metal ion. E.g.
ethylenediamine (commonly abbreviated as “en”) has a chain of four atoms

( N-C-C-N ), so it forms a five membered ring, with the two electron-donating N

atoms to the metal atom. Such ligands seem to grab the metal ion like claws, so a
complex ion that contains them is also called a chelate (pronounced KEY-late; from
the Greek word, Chele, meaning “claw”).

H2N-CH2-CH2-NH2

NWAKIFE, C. N.
4
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

ethylenediamine
The two nitrogen atom can coordinate with a metal as shown below:
H2
C
H2C
NH2 H
2
H2N N CH2
M
H2N N CH2
NH2 H2
H2C
CH2 Each ethylenediamine molecule provides two N donor atoms
and is therefore a bidentate ligand.

C. Ploydentate Ligands
These have more than two donor atoms. E.g. ethylenediaminetetraacetate ion
(EDTA).

USES OF EDTA
1. EDTA is used to treat metal poisoning
2. It is used to form a very stable complex ion with lead, which is removed from blood
and excreted from the body.
3. EDTA is also used to clean up spills of radioactive metals.

Ambidentate ligand is a special type of ligand that has more than one possible attachment
site but does not generally act as a multidentate ligand. For example, the ambidentate ligand
SCN- typically attaches to a metal at S or N, but not both at the same time.

Bidentate and polydentate ligands are also called chelating agents because of their ability to
hold the metal atom like a claw. One example is ethylenediaminetetraacetate ion (EDTA).
Six donor atoms enable EDTA to form a very stable complex ion with lead, which is
removed from the blood and excreted from the body. Bidentate and polydentate ligands give
rise to rings in complex ions.

NWAKIFE, C. N.
5
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

NAMES OF SOME NEUTRAL AND ANIONIC LIGANDS

A. Monodentate/ Anionic Ligands
Common Name IUPAC Name Formula Structure
hydrido hydrido H-
fluoro fluoro F- -
F
chloro chloro Cl- -
Cl
bromo bromo Br-
iodo iodo I-
nitride nitrido N3-
azido azido N3-
oxo oxido O2-
cyano cyano CN- C N -
thiocyano thiocyanato-S(S-bonded) SCN- -
S C N
isothiocyano thiocyanato-N(N-bonded) NCS-
hydroxo hydroxo OH- -
O H
nitrito nitrito-O (O-bonded) ONO-
nitrosyl nitrosyl NO+
nitro nitrito-N (N-bonded) NO2-
amido azanido NH2-
imido azanediido NH2-

B. Monodentate/ Neutral ligands

Common Name IUPAC Name Formula Structure
aqua/aquo aqua/aquo H2O O

H H
carbonyl carbonyl CO C O
thiocarbonyl thiocarbonyl CS
methyl isocyanide methyl isocyanide CH3NC
phosphine phosphane PR3
pyridine pyridine C5H5N
ammine ammine NH3 N
H H
H
methylamine methylamine MeNH2

C. Bidentate/Chelating Ligands
Common Name IUPAC Name Abbreviation Formula
ethylenediamine 1,2-ethanediamine en H2N-CH2-CH2-NH2

NWAKIFE, C. N.
6
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

oxalate ion 2-
O O
C C
O O

D. Tridentate Ligands/Chelating Amine

Common Name IUPAC Name Abbreviatio Formula
n
diethylenetriamine 2,2- dien NH2CH2CH2NHCH2CH2N
diaminodiethylamine H2
or H2C CH2 CH2 CH2
1,4,7-triazaheptane NH2 NH2
N
H

E. Tetradentate/ Chelating Amine

Common Name IUPAC Name Abbre. Formula
triethylenetetraamine 1,4,7,10- trien NH2CH2CH2NHCH2CH2NHCH2CH2NH2
tetraazadecane
β, β´, β´´- β, β´, β´´-tris(2 tren NH2CH2CH2NCH2CH2NH2
triaminotriethylamine aminoethyl)am
CH2CH2NH2
ine

F. Pentadentate/ Chelating Amine

Common Name IUPAC Name Formula
tetraethylepentamine 1,4,7,10,13- NH2CH2CH2NHCH2CH2NHCH2CH2NHCH2CH2NH2
pentaazatridecane

G. Hexadentate/ Chelating Amine

Common Name IUPAC Name Abbreviation Formula
-
OOCH2C CH2COO-
ethylenediaminetetr 1,2- EDTA
aacetate ethanediyl(diniyrilo)te NCH2CH2N
-
traacetate OOCH2C CH2COO-

H. Multidentate/ Chelating Ligands

Common Name IUPAC Name Abbrevia Formula Structure
tion
O O
acetylacetonato 2,4-pentanediono acac CH3COCHCOCH3-
C C
H3C CH3
C
H
2,2´-bipyridine 2,2´-bipyridyl bipy C10H8N2 N N

NWAKIFE, C. N.
7
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

N N
1,10- 1,10- phen, C12H8N2
phenanthroline diaminophenanthren o-phen
o - phenanthroline e
oxalate oxalate ox C2O42- O O
C C
O O
dialkyldithiocarba dialkylcarbamodithi dtc S2CNR2 -
S R
mato oato
C N
S R
1,2- 1,2- dppe Ph2PC2H4PPh2
bis(diphenylphos ethanediylbis(diphen P
phino)ethane ylphosphane) H2C
CH2
P

Me Me
o- 1,2- diar C6H4(As(CH3)2)2
phenylenebis(dim phenylenebis(dimeth Me As As Me

ethylarsine) ylarsane)

dimethylglyoxima butanediene dioxime DMG HONCC(CH3)C(C N CH3

HO
te H3)NO-
OH
H3C N

OXIDATION NUMBER OF METAL IN COORDINATION COMPOUNDS

Oxidation number often called the oxidation state is an indicator of the degree of oxidation
(loss of electron) of an atom in a chemical compound. It is also referred to as the primary
valence. Oxidation number of metal in coordination compound is the net charge on the
central metal atom.

For example,
In [PtCl6]2- ion, each chloride ion has an oxidation number of -1, so the oxidation number of
Pt must be +4.i.e.
[PtCl6]2-
Pt + (-1× 6) = -2
Pt -6 = -2
Pt = -2 + 6
Pt = +4

NWAKIFE, C. N.
8
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

If the ligands do not bear net charges, the oxidation number of the metal is equal to the
charges of the complex ion.

Thus, in [Cu(NH3)4]2+ each NH3 is neutral, so the oxidation number of Cu is +2.

i.e. [Cu(NH3)4]2+
Cu + (0× 4) = +2
Cu + 0 = +2
Cu = +2

OXIDATION NUMBER OF COMPLEX ION IN COORDINATION COMPOUNDS

In coordination compounds, the net charge of a complex ion is the sum of the charges on the
central metal atom and its surrounding ligands.
i.e. Charge of complex ion = charge of metal ion + total charge of ligands
Therefore, Charge of metal ion = charge of complex ion - total charge of ligands

For example
1. [PtCl6]?
The oxidation number of Pt is said to be +4.
Therefore, the sum of the charges of the metal atom and ligand will give the net charge of
the complex ion.
The net charge of the complex ion = +4 + (-1 × 6)
= +4 – 6
= -2
Therefore, the net charge of the complex ion is -2

2. [Cr(NH3)6](NO)3]
The oxidation number of chromium is said to be +3.
The net charge of the complex ion = +3 + (0 × 6)
= +3 + (0)
= +3
Therefore, the net charge of the complex ion is +3.
Exercise
Specify the oxidation number of the central metal atom and the complex ion in each of the
following coordination compounds:
1. [Ru(NH3)5(H2O)]Cl2
2. [Cr(NH3)6](NO3)3
3. [Fe(CO)5]
4. K4[Fe(CN)6]
5. K[Au(OH)4]

NWAKIFE, C. N.
9
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

NOMENCLATURE RULES FOR COORDINATION COMPOUNDS

Coordination compounds were originally named after the person who first compared them or
from their colour, and some of these common names are still used, but most coordination
compounds are named systematically through a set of rules. The important rules for writing
the formulas of coordination compounds, the first being the same for writing formulas of any
ionic compound (i.e. a chemical compound comprising ions held together by electrostatic
forces termed ionic or electrovalent bonding). The compound is neutral overall, but consists
of positively charged ions called cations and negatively charged ions called anions. E.g. NaCl
(sodium chloride), Mg(OH)2 (magnesium hydroxide).

These set of rules are:

1. The cation (positive ion) is named or written before the anion (negative ion), as in other
ionic compounds. The rule holds regardless of whether the complex ion bears a net
positive or negative charge. If the counter ion bears the positive charge, it is named first
despite its attachment to a complex ion and vice versa. Also, it does not matter, if it is the
complex ion that has the positive or negative charge.

For example, in K3[Fe(CN)6] and [Co(NH3)4Cl2]Cl, we name the K+ and

[Co(NH3)Cl2]+cations first respectively. i.e.
a. K3[Fe(CN)6] 3K+ + [Fe(CN)6]3+
potassium hexacyanoferrate(III)

b. [Co(NH3)4Cl2]Cl [Co(NH3)4Cl2]+ + Cl-

tetraamminedichlorocobalt(III) chloride

c. [Ag(NH3)2]Cl [Ag(NH3)2]+ + Cl-

diamminesilver(I) chloride

2. In a coordination compound, the charge of the cation(s) is balanced by the charge of the
anion(s).

3. Within a complex ion, the ligands are named in alphabetical order according to the name
of the ligand, not the prefix-although exceptions to this rule are common, and the

NWAKIFE, C. N.
10
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

metal ion is name last; but in chemical formulas, the metal ion is written first, followed
by the ligands which are equally arranged in alphabetical order.

For example,
a. tetraamminecopper(II) sulphate
[Cu(NH3)4]SO4

b. Pt(NH3)BrCl(CH3NH2)
amminebromochloromethylamineplatinum(II)

c. hexaaminecobalt(III) chloride
[Co(NH3)6]Cl3

d. tetraaminedichlorocobalt(III) ion
[Co(NH3)4Cl2]+
tetraamine alphabetized by “a” and dichloro by “c”, not by the prefixes.

4. In writing the chemical formula of a coordination compound, the complex ion (the inner
coordination sphere) is enclosed in square bracket with the counter ion written outside
the square bracket, be it a cationic counter ion or an anionic counter ion.
Note
a. The whole complex ion maybe a cation or an anion i.e. a cationic complex or an
anionic complex.
b. In a coordination compound, a complex cation has anionic counter ions, and a
complex anion has a cationic counter ions.
c. Some coordination compounds have a complex cation and a complex anion e.g.
[Co(NH3)5Br]2[Fe(CN)6]. In this compound, the complex cation is [Co(NH3)5Br]2+,
with Co3+, and the complex anion is [Fe(CN)6]4-, with Fe2+. Two of the complex
cations i.e. [Co(NH3)5Br]2+ are required to counter the 4- charge on the complex
anion.

5. In naming, the only space in the name appears between the cation and the anion.

NWAKIFE, C. N.
11
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

6. When writing the chemical formula of a complex ion, the central metal is written first
followed be the neutral ligand(s) and then the anionic ligand(s) which are arranged in
alphabetical order.

7. Anionic ligands are given an o-suffix. Neutral ligands generally have the molecule name,
but there are a few exceptions. Coordinated water is called aqua/aquo and coordinated
ammonia is called ammine. Anionic ligands drop the –ide and add –o after the root
name; thus the name fluoride for the F- ion becomes the ligand name fluoro.
ANIONIC LIGANDS NEUTRAL LIGANDS
Name Formula Name Formula
fluoro F- aqua/aquo H2O
chloro Cl- ammine NH3
bromo Br- carbonyl CO
iodo I- nitrosyl NO
hydroxo OH- methylamine CH3NH2
Cyano CN- nitro NO2-
sulfato SO42- oxo O2-
carbonato CO32-
ethylenediamine NH2CH2CH2NH2(e
n)

8. When several ligands of a particular kind are present, the Greek prefixes are used to
indicate the number of ligands. Monodentate ligands use the prefixes di-, tri-, tetra-,
penta-, and hexa- to indicate 2, 3, 4, 5, and 6 ligands respectively. The prefixes do not
affect the alphabetical order i.e., prefixes are ignored when alphabetizing ligands.

For example
[Co(NH3)4Cl2]+
tetraammine denotes four NH3, and dichloro denotes two Cl-

9. If the ligand name contains prefixes or is complicated, it is set off in parenthesis, and the
second set of prefixes (all ending in -is) is used.
2 di bis
3 tri tris
4 tetra tetrakis
5 penta pentakis
6 hexa hexakis
7 hepta heptakis
8 octa octakis

NWAKIFE, C. N.
12
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

9 nona nonakis
10 deca decakis
For example
a. [Co(NH2CH2CH2NH2)2Cl2]+or [Co(en)2Cl2]+
dichlorobis(ethylenediamine)cobalt(III) ion
The ligand ethylenediamine already contains di-; therefore, if two such ligands are
present the name is bis(ethylenediamine). Also when three or four of such ligands
exist, the name is tris(ethylenediamine) or tetrakis(ethylenediamine) respectively.

b. [Fe(NH4C5C5H4N)3]2+
tris(bipyridine)iron(II) ion

10. The oxidation state of the central metal ion is given by a Roman numeral (in parenthesis)
following the name of the metal only if the metal ion can have more than one oxidation
state.

For example
a. [Cr(NH3)4Cl2]+
tetraaminedichlorochromium(III) ion
The Roman numeral III is used to indicate the +3 oxidation state of chromium in the
[Cr(NH3)4Cl2]+ complex ion.

b. Na3[AlF6] 3Na+ + [AlF6]3-

sodium hexafluoroaluminate
The complex ion is [AlF6]3-. There are six (hexa-) F- ions (fluoro) as ligands, so we have
hexafluoro. The complex ion is an anion, so the ending of the metal ion (aluminium)
must be changed to –ate: hexafluoroaliminate. Aluminium has only the +3 oxidation
state, so we do not use a Roman numeral. The positive counter ion is named first and
separated from the anion by a space.

11. When the complex ion is an anion (negatively charged), its name ends in –ate. The name
of the following metal is derived from the sources of their symbols. The symbols of some

NWAKIFE, C. N.
13
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

elements are gotten from the element’s latin name. Therefore, it is the latin name that
will have the suffix -ate.
Metal Name of Metal in Anionic Complex
Aluminium Aluminate
Chromium Chromate
Cobalt Cobaltate
Tungsten Tungstate
Zinc Zincate
Molybdenum Molybdate
Nickel Nickelate
Copper Cuprate
Gold Aurate
Silver Argentite
Iron Ferrate
Lead Plumbate
Manganese Manganate
Tin Stannate

For example
a. K[Pt(NH3)Cl5] i.e. K+ + [Pt(NH3)Cl5]-
potassium amminepentachloroplatinate(IV)
The anion is [Pt(NH3)Cl5]-, the Roman numeral (IV) is used to indicate the oxidation
state of the platinum.

b. K4[Fe(CN)6]i.e. 4K+ + [Fe(CN)6]4-

The anion is [Fe(CN)6]4-, therefore, the name of the compound is potassium
hexacyanoferrate(II)

c. Na4[FeBr6]i.e. 4Na+ + [FeBr6]4-

The anion is [FeBr6]4-, therefore, the name of the compound is sodium
hexabromoferrate(II)

SYSTEMS FOR DESIGNATING CHARGE OR OXIDATION NUMBER:

Two systems exist for designating charge or oxidation number and they are;
1. The stock systemputs the calculated oxidation number of the metal ion as a Roman
numeral in parentheses after the name of the metal. This is the more common

NWAKIFE, C. N.
14
 INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

convention, although there are cases in which it is difficult to assign oxidation

numbers.

2. The Ewing-Basset system puts the charge on the coordination sphere in parentheses
after the name of the metal. This convention is used by Chemical Abstracts and offers
an unambiguous identification of the species.
In either case, if the charge is negative, the suffix-ate is added to the name of the coordination
sphere.
For example
a. [Pt(NH3)4]2+
tetraamineplatinum(II) or tetraammineplatinum(2+)

b. [PtCl4]2-
tetrachloroplatinate(II) or tetrachloroplatinate(2-)

c. [PtCl6]2-
hexachloroplatinate(IV) or hexachloroplatinate(2-)

12. The prefixes cis- and trans- designate adjacent and opposite geometric locations.

For example
a. cis- and trans-diaamminedichloroplatinum(II)
H3N Cl H3 N Cl

Pt Pt
H3N Cl Cl NH3
Cis (Cisplatin) Trans
[Pt(NH3)3Cl2] or [PtCl2(NH3)3]

 It is used for cancer treatment.

 Bridging ligands between two metal ion.
b. tris(tetraamine-µ-dihydroxocobalt)cobalt(6+)
[Co(Co(NH3)4(OH)2)3]6+

NWAKIFE, C. N.
15
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

c. µ-amido-µ-hydroxobis(tetraaminecobalt)(4+)
[(NH3)4Co(OH)(NH2)Co(NH3)4]4+
4+
H
NH3 NH3
H3N N

Co Co
H3N O
NH3 NH3
H

Bridging amide and hydroxide ligands. In µ-amido-µ-hydroxobis(tetraaminecobalt)(4+)

[(NH3)4Co(OH)(NH2)Co(NH3)4]4+.

Problem/Solution
1. Write the systematic names of these compounds
a. Ni(CO)4
Solution
The CO ligands are neutral species and the nickel atom bears no net charge. The
name of the compound is tetracarbonylnickel(0). More commonly, the compound
is called nickel tetracarbonyl.
Answer –tetracarbonylnickel(0)

b. [Co(NH3)4Cl2]Cl i.e. [Co(NH3)4Cl2]+ + Cl-

Solution
Starting with the cation, each of the two chloride ligand bears a negative charge
and the ammonia molecules are neutral. Thus, the cobalt atom must have an
oxidation number of +3 (to balance the chloride anion)
i.e.,
 Four ammonia ligands (tetraammine)
 Two chloride ligands (dichloro; prefix = di and ligand name = chloro)
 A cobalt ion with a +3 oxidation number
i.e. Co + (0 × 4) + (-1 × 2) + (-1) = 0
Co + (0 ) + (- 2) + (-1) = 0
Co - 2-1 = 0
Co - 3 = 0

NWAKIFE, C. N.
16
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

Co = + 3
 One chloride ion as the counter ion
 Remember that the only space that exists in the name of a coordination
compound is between the complex ion and the counter ion or anions and
cations as the case maybe.
Answer –tetraamminedichlorocobalt(III) chloride

c. K3[Fe(CN)6] i.e. 3K+ + [Fe(CN)6]3-

Solution
The complex ion is the anion and it bears three negative charges. Thus, the iron
atom must have an oxidation number of +3. This compound is commonly called
potassium ferricyanide.
 Six cyano ligands (hexacyano)
 An iron ion with a +3 oxidation number
i.e. (+1 × 3) + Fe + (-1 × 6) = 0
(+3) + Fe + (-6) = 0
Fe = +6 -3
Fe = + 3
 Remember that the only space that exists in the name of a coordination
compound is between the complex ion and the counter ion or anions and
cations as the case maybe.
Answer – potassium hexacyanoferrate(III)

d. [Cr(en)3]Cl3 i.e. [Cr(en)3]3+ + 3Cl-

Solution
As we noted earlier, en is the abbreviation for the ligand ethylenediamine.
Because there are three en-groups present and the name of the ligand already
contain di-, the name of the compound is tris(ethylenediamine)chromium(III)
chloride.
 Three ethylenediamine ligands [tris(ethylenediamine)]
 A chromium ion with a +3 oxidation number
i.e. Cr + (0 × 3) + (-1 × 3) = 0
Cr + (0 ) + (-3) = 0
Cr - 3 = 0
Cr = + 3

NWAKIFE, C. N.
17
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

 Three chloride ions as the counter ions

 Remember that the only space that exists in the name of a coordination
compound is between the complex ion and the counter ion or anions and
cations as the case maybe.
Answer –tris(ethylenediamine)chromium(III) chloride

2. Write the formula for these compounds

a. Pentaamminechlorocobalt(III) chloride
Solution
[Co(NH3)5Cl]2+ + 2Cl- [Co(NH3)5Cl]Cl2
The complex cation contains five NH3 groups, a chloride ion, and a cobalt ion
with a +3 oxidation number. The net charge on the complex cation must be 2+.
Therefore, the formula for the compound is [Co(NH3)5Cl]Cl2.
 Five ammonia (NH3)5 ligands (pentaammine)
 One chloride ligands (chloro)
 Co3+ ion
 The combination of the central metal ion and ligands gives a complex ion
with an overall +2 charge i.e. [+3 + (0 × 5) + (-1)]
[+3 -1)] = +2
 Hence, two Cl- counter ions are needed to balance the charge on the
complex ion. Therefore, the compound is [Co(NH3)5Cl]Cl2
 Remember that the neutral ligands are written first, follow by the anionic
ligands which are arranged alphabetically.
Answer – [Co(NH3)5Cl]Cl2

b. dichlorobis(ethylenediamine)platinum(IV)nitrate
Solution
[Pt(en)2Cl2]2+ + 2NO3- [Pt(en)2Cl2](NO3)2
There are two chloride ions, two ethylenediamine groups, and a platinum ion with
an oxidation number of +4 in the complex cation. Therefore, the formula for the
compound is [Pt(en)2Cl2](NO3)2.
 Two chloride ligands (dichloro)

NWAKIFE, C. N.
18
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

 Two ethylenediamine ligands [bis(ethylenediamine)]

 Pt4+ ion
 The combination of the central metal ion and ligands gives a complex ion
with an overall +2 charge i.e. [+4 + (-1 × 2) + (0 × 2)]
[+4 -2) + 0] = +2
 Hence, two nitrate (NO3-) counter ions are needed to balance the charge on
the complex ion. Therefore, the compound is [Pt(en)2Cl2](NO3)2.
 Remember that the neutral ligands are written first, follow by the anionic
ligands which are arranged alphabetically.

Answer –[Pt(en)2Cl2](NO3)2

c. Sodium hexanitrocobaltate(III)
Solution
3Na+ + [Co(NO2)6]3+ Na3[Co(NO2)6]
The complex anion contains six nitro groups and a cobalt ion with an oxidation
number of +3. Therefore, the formula for the compound is Na3[Co(NO2)6].
Answer –Na3[Co(NO2)6]

3. What is the systematic name of [Co(en)2Cl2]NO3?

Solution
Listed alphabetically, there are two Cl- (dichloro) and two en [bis(ethylenediamine)]
as ligands. The complex ion is a cation, so the metal is unchanged, but we specify its
oxidation state because cobalt can have several. One NO3- balances the 1+cation
charge: with 2- for two Cl- and 0 for two en, the metal must be cobalt(III). The word
nitrate follows a space.
Answer – dichlorobis(ethylenediamine)cobalt(III) nitrate.

4. What is the formula of tetraaminebromochloroplatinum(IV) chloride?

Solution
The central metal ion is written first, followed by the neutral ligands and then (in
alphabetical order) by the negative ligands. Tetraamine is four NH 3, bromo is one Br-,

NWAKIFE, C. N.
19
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

chloro is one Cl-, and platinum (IV) is Pt4+, so the complex ion is [Pt(NH 3)4BrCl]2+. Its
2+ charge is the sum of 4+ for Pt 4+, 0 for four NH3,1- for one Br-, and 1- for Cl-. To
balance the 2+ charge, we need two Cl- counter ions.
Answer – [Pt(NH3)4BrCl]Cl2

5. What is the formula of hexaaminecobalt(III)tetrachloroferrate(III)

Solution
The compound consists of two different complex ions. In the cation, hexaamine is six
NH3 and cobalt(III) is Co3+, so the cation is [Co(NH3)6]3+. The 3+ charge is the sum of
3+ for Co3+ and 0 for six NH3. In the anion, tetrachloro is four Cl -, and ferrate(III) is
F3+, so the anion is [Fe(Cl4)]-. The 1- charge is the sum of 3+ for Fe3+ and 4- for four
Cl-. In the neutral compound, one 3+ is balanced by three 1- anions.
Answer – [Co(NH3)6][FeCl4]3

Exercise
1. What is the systematic name of [Cr(H20)4Cl2]Cl?
2. What is the formula for this compound: tris(ethylenediamine)cobalt(III)sulfate?
3. What is the name of [Cr(H2O)5Br]Cl2?
4. What is the formula of barium hexacyanocobaltate(III)?
5. Name the following coordination complexes:
a. Cr(NH3)3Cl3
b. Pt(en)Cl2
c. [Pt(ox)2]2-
d. [Cr(H2O)5Br]2+
e. [Cu(NH2CH2CH2NH2)Cl4]2-
f. [Fe(OH)4]-

6. Give the structures of the following coordination complexes:

a. tris(acetylacetonato)iron(iii)
b. hexabromopaltinate(2-)
c. potassium diamminetetrabromocobaltate(iii)
d. tris(ethylenediamine)copper(ii) sulfate
e. hexacarbonylmanganese(i)perchlorate
f. ammonium tetrachlororuthenate(1-)

NWAKIFE, C. N.
20
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

3. GEOMETRY OF COORDINATION COMPOUNDS

The geometry (shape) of a complex ion is related (or dependant) on the coordination
number, and the nature of the metal ion. The most common coordination number is 6,
with the existence of 2 and 4. Some higher coordination numbers are also known. The
four different geometric arrangements for metal atoms with monodentate ligands in some
complex ion are as shown below:
1. Linear geometry
2. Tetrahedral geometry
3. Square planar geometry
4. Octahedral geometry

The structure and coordination number of the metal atom relate to each other as follows:
Coordinator Shape Structure Example
Number
2 Linear L M L
[CuCl2]-, [Ag(NH3)2]+, [AuCl2]-
4 Tetrahedral L [Cu(CN)4]3-, [Zn(NH3)4]2+, [CdCl4]2-,
[MoCl4]2-
M
L
L
L
L L
4 Square planar [Ni(CN)4]2-, [PdCl4]2-, [Pt(NH3)4]2+,
M [Cu(NH3)4]2+
L L
L
6 Octahedral L [Ti(H2O)6]3+, [V(CN)6]4-,
L M L
[Cr(NH3)4Cl2]+,[Mn(H2O)6]2+
L [FeCl6]3-,[Co(en)3]3+
L

M=metal
L=monodentate ligand

Coordination Number = 2
A complex ion with a coordination number of 2, such as [Ag(NH 3)2]+ has linear
geometry. The complex ion is formed by the reaction between Ag + ions and ammonia.
Other examples are [CuCl2]-and [Au(CN)2]-. d10 metal ions with two ligands have linear
geometry.

For example
a. [Ag(NH3)2]+
Ag + (0×2) = +1

NWAKIFE, C. N.
21
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

Ag = +1 (oxidation number)
It is formed by the reaction of Ag+ ion and two ammonia (NH3) molecules.

H3N Ag NH3 . It has a coordination number of number of 2 with a linear

geometry.
Ag has an atomic number = 47→ 1s22s22p63s23p64s23d104p65s14d10 (extra stability
associated with half-filled and completely filled d-subshells).

For Ag+, it has lost one electron, therefore, Ag+ = 46→1s22s2s2p63s23p64s23d104p64d10

b. [CuCl2]-
Cu + (-1×2) = -1
Cu + (-2) = -1
Cu = -1 + 2
Cu = +1 (oxidation number)

It is formed by the reaction of Cu + ion and two chloride atoms (Cl-).

Cl Cu Cl
. It has a coordination number of number of 2 with a linear
geometry.
Cu has an atomic number = 29→ 1s22s22p63s23p64s13d10 (extra stability associated
with half-filled and completely filled d-subshells).

For Cu+, it has lost one electron, therefore,

Cu+ = 28→1s22s2s2p63s23p63d10

Coordination Number = 4
There are two types of geometries with coordination number of 4 namely:
1. Tetrahedral geometry
2. Square planar geometry

Tetrahedral Geometry
Most of the d5 and d10 metal ions with four ligands usually form tetrahedral complex ions
e.g. [Zn(NH3)4]2+ and [CoCl4]2- ions.
For example
1. [Zn(NH3)4]2+

NWAKIFE, C. N.
22
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

Zn + (0×4) = +2
Zn = +2
Zn = 30 →1s22s2s2p63s23p64s23d10
Zn2+ = 30-2 = 28 →1s22s2s2p63s23p63d10

2. [Cu(CN)4]3-
Cu + (-1×4) = -3
Cu + (-4) = -3
Cu = -3 + 4
Cu = +1
Cu = 29 →1s22s2s2p63s23p64s13d10
Cu+ = 29-1 = 28 →1s22s2s2p63s23p63d10

3. [Cd(Cl)4]2-
Cd + (-1×4) = -2
Cd + (-4) = -2
Cd = -2 + 4
Cd = +2
Cd = 48 → 1s22s22p63s23p64s23d104p65s24d10
Cd2+ = 48-2 = 46 → 1s22s22p63s23p64s23d104p64d10

Square Planar Geometry

Most d8 and d9 metal ions with four ligands form square planar complex ions. E.g.
[Pt(NH3)4]2+ ion.

For example
1. [Cu(NH3)4]2+
Cu + (0×4) = +2
Cu = +2

Cu = 29 →1s22s2s2p63s23p64s13d10
Cu2+ = 29-2 = 27 →1s22s2s2p63s23p63d9

2. [Ni(CN)4]2-
Ni + (-1×4) = -2
Ni + (-4) = -2

NWAKIFE, C. N.
23
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

Ni = -2 + 4
Ni = +2
Ni = 28 →1s22s2s2p63s23p64s23d8
Ni2+ = 28-2 = 26 →1s22s2s2p63s23p63d8

Square planar complex ions with two different monodentate ligands can also exhibit
geometric isomerism. The structure below shows the cis- and trans- isomers of
diamminedichloroplatinum(II). Although the types of bonds are the same in both isomers
(two Pt-N and two Pt-Cl bonds), the spatial arrangements are different. These two
isomers have different properties (melting point, boiling point, colour, solubility in
water, and dipole moment).

H3N Cl Cl NH3

Pt Pt
H3N Cl H3N Cl
Cis Trans

The two Cl atoms are adjacent to each other in the cis isomer and diagonally across from
each other in the trans isomer.

Coordination Number = 6
Complex ions with a coordination of 6 all have octahedral geometry. Geometric
isomerism is possible in octahedral complexes when two or more different ligands are
present. An example is the tetraamminedichlorocobalt(III) ion shown below. The two
geometric isomers have different colours and other properties even though they have the
same ligands and the same number and types of bonds.
NH3 NH3 Cl Cl
Cl NH3 Cl NH3 Cl NH3 H3N NH3
Co Co Co Co
Cl NH3 H3N Cl H3N NH3 H3N NH3
NH3 NH3 NH3 Cl
(a) (b) (c) (d)

NWAKIFE, C. N.
24
INTRODUCTION TO COORDINATION CHEMISTRY CHM 212

The (a) cis and (b) trans isomers of tetraamminedichlorocobalt(III) ion. The structure
shown in (c) can be generated by rotating that in (a), and the structure shown in (d) can
be generated by rotating that in (b). The ion has only two geometric isomers, (a) [or (c)]
and (b) [or (d)].

In addition to geometric isomerism, certain octahedral complex ions can also exhibit
optical isomerism (that is, give rise to optical isomers). The structures below show the cis
and trans isomers of dichlorobis(ethylenediamine)cobalt(III) ion and their mirror images.
Mirror Mirror
Cl Cl Cl
Cl

Co Co Co
Co
Cl Cl Cl
Cl

(a) Cis (b) Trans

Careful examination reveals that the trans isomers and its mirror image are
superimposable, but the cis isomers, and its mirror image are not. Therefore, the cis
isomer and its mirror image are optical isomers or enantiomers. It is interesting to note
that unlike the case in most organic compounds, there are no asymmetric carbon atoms in
these compounds.

Note
In the figure above, the (a) is cis and (b) is trans isomers of
dichlorobis(ethylenediamine)cobalt(III) ion and their mirror images. If you could rotate
the mirror image in (b) 90o clockwise about the vertical position and place it over the
trans isomer, you would find that the two are superimposable. No matter how you rotated
the cis isomer and its mirror image, however, you could not superimpose one on the
other.

NWAKIFE, C. N.
25