INTRODUCTION TO COORDINATION

CHEMISTRY

Introduction

Transition metals differ from main group metals in several key properties. One of the
more interesting aspects of transition metals is their ability to form coordination
compounds. Coordination compounds are formed between a metal atom or ion and a
molecule with one or more unshared electron pairs, called a ligand. Ligands may be
classified according to the number of donor atoms they contain. A monodentate ligand
donates a single electron pair to the metal or metal ion. Common examples of
monodentate ligands include NH3, H2O, NO2-, and CN-. A bidentate ligand, as the name
suggests, donates two electron pairs to the metal or metal ion. A good example is
ethylenediamine, NH2CH2CH2NH2.

Anions as well as neutral molecules may act as ligands. If one or more neutral molecules
coordinate to metal ion, the resulting species retains the charge of the transition metal ion
and is called a complex ion. For example, most transition metal ions form complex ions
with water molecules when in aqueous solution. Examples include [Co(H2O)]6]3+ and
[Ni(H2O)6]2+. If one or more anions coordinate to a metal ion, a complex ion with an
overall negative charge may result. Examples include [Co(NO2)6]3- and [Fe(CN)6]4-.

In writing formulas for complex ions and coordination compounds, the molecules inside
the brackets represent ligands physically coordinated to the metal ion. Anything outside
of the brackets is present for charge balance. Therefore the formulas [Co(H2O)6]Cl3 and
[Ni(H2O)6]Cl3 represent neutral compounds in which the chloride ions are present for
charge balance. The formulas K3[Co(NO2)6] and K4[Fe(CN)6] represent molecules
containing negatively charged complex ions with potassium ions present for charge
balance.

Most transition metal ions form complex ions with water molecules when in aqueous
solution. Such compounds readily form because water is present in excess. However,
water is not a particularly strong ligand. Such complexes are prone to substitution
reactions in which the water molecules are successively replaced with other ligands.
Such reactions are often accompanied by a change in the color of the solution. For
example, the green [Ni(H2O)6]2+ ion is formed when many nickel (II) salts are dissolved
in water. Upon the addition of concentrated NH3, however, the color changes to blue as
[Ni(NH3)6]2+ ion is formed.

[Ni(H2O)6]2+ + 6NH3  [Ni(NH3)6]2+ + 6H2O

Complexes may be classified as inert or labile, depending upon the speed at which
substitution reactions occur. Labile complexes undergo substitution reactions rapidly,

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whereas inert complexes undergo substitution reactions slowly. Octahedral Co 3+ and Cr3+
complexes are inert, making it possible to isolate a large number of complexes containing
these metal ions.

In this laboratory, you will explore some of the coordination chemistry of copper, iron,
cobalt, and nickel. The chemistry of these transition metals is discussed in the sections
that follow.

The Chemistry of Copper

The two most important oxidation states of copper are the +1 (cuprous) and +2 (cupric).
The +2 ion is more stable and by far the most common. Commonly encountered copper
salts include copper sulfate pentahydrate and copper chloride dihydrate, which have the
formulas CuSO45H2O and CuCl22H2O. The former is pale blue in color, and the latter
is blue-green in color.

Copper sulfate pentahydrate contains copper(II) in a geometry best described as distorted

octahedral. The copper(II) is bound to four water molecules in a square-planar geometry
and two oxygen atoms from two sulfate ions. This salt dissolves in water to produce the
pale-blue [Cu(H2O)6]2+ ion, in which two of the water molecules are less tightly held and
have longer bond distances. The blue-green color of cobalt chloride dihydrate is due to
the presence of some CuCl42-, which is yellow in color and has a square planar geometry.
Concentrated solutions of copper chloride may appear blue-green in color, but dilution
results in the formation of the pale-blue [Cu(H2O)6]2+ ion.

Addition of NH3 to solutions containing the [Cu(H2O)6]2+ ion results in successive

replacement of the first four H2O molecules. Replacement of the fifth and six water
molecules does not occur to an appreciable extent in aqueous solution, and replacement
of the sixth only occurs in liquid ammonia.

[Cu(H2O)6] + NH3  [Cu(H2O)5(NH3)]2+ + H2O

[Cu(H2O)5(NH3)]2+ + NH3  [Cu(H2O)4(NH3)2]2+ + H2O
[Cu(H2O)4(NH3)2]2+ + NH3  [Cu(H2O)3(NH3)3]2+ + H2O
[Cu(H2O)3(NH3)3]2+ + NH3  [Cu(H2O)2(NH3)4]2+ + H2O

Addition of HCl to a solution containing the [Cu(H2O)6]2+ ion results in the formation of
[CuCl4]2- which, as previously mentioned, is yellow in color and has square planar
geometry. Salts containing this ion may be isolated with bulky cations, as in
(NH4)2[CuCl4]. Addition of OH- to [Cu(H2O)6]2+ results in the initial formation of solid

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Cu(OH)2, but with further additions the solid dissolves to form the complex ion
[Cu(OH)4]2-. Addition of NO2- to a solution containing the [Cu(H2O)6]2+ ion results in the
formation of a solution which probably contains the [Cu(NO2)4]2- ion.

The Chemistry of Iron

The two most stable oxidation states of iron are the +2 (ferrous) and +3 (ferric). One of
the most commonly encountered ferrous salts is ferrous sulfate hexahydrate. The solid
salt is pale-green in color and dissolves in water to give pale green solutions. However,
the ferrous ion is readily oxidized to the ferric ion by atmospheric oxygen, and solutions
slowly turn yellow due to this oxidation.

Salts containing the [Fe(H2O)6]3+ ion are colorless or pale violet in color. However, in
aqueous solution the ferric ion quickly hydrolyzes in water to the give yellow-brown
color more usually associated with iron.

[Fe(H2O)6]3+ + H2O  [Fe(H2O)5(OH)] + H3O+

[Fe(H2O)5(OH)] + H2O  [Fe(H2O)4(OH)2] + H3O+

As a result, such solutions are quite acidic. Strongly acidic solutions are necessary to
prevent this hydrolysis. The ferric ion forms a well-known blood-red complex ion
[Fe(H2O)5(SCN)]2+ when SCN- is added. The color change is quite striking, even in dilute
solutions, and serves as a chemical test for ferric ion.

The Chemistry of Cobalt

The two most stable oxidation states of cobalt are the +2 (cobaltous) and +3 (cobaltic).
The cobaltous ion is labile and may have either a tetrahedral or octahedral geometry.
Common salts include cobalt chloride hexahydrate and cobalt nitrate hexahydrate, which
have the formulas [Co(H2O)6]Cl2 and [Co(H2O)6](NO3)2. In solution, cobalt(II) forms the
octahedral [Co(H2O)6]2+ ion, which is pale pink in color. Addition of concentrated HCl
results in the formation of the complex ion [CoCl4]2-, which has a tetrahedral geometry.
Addition of the SCN- ion results in the formation of [Co(SCN)4]2-, which is also
tetrahedral.

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 The Chemistry of Chromium

Chromium exists in a wide variety of oxidation states. Common oxidation states include
+2, +3, and +6. The +2 ion is labile, and in aqueous solution forms the blue [Cr(H2O)6]2+
ion. The +3 ion is kinetically inert, and therefore is has been widely studied with many
different compound isolated.

Two common chromium salts include chromium potassium sulfate and chromium
chloride. Both are hydrates, with the formulas KCr(SO4)212H2O and CrCl36H2O. The
sulfate salt dissolves in water to give the [Cr(H2O)6]3+ ion, which is violet in color.
However, the chloride salt does not dissolve to give the same violet [Cr(H2O)6]3+ ion.
Due to the inertness of the +3 ion, one or more chlorides remain coordinated in aqueous
solution and complex ions such [Cr(H2O)4Cl2]+ or [Cr(H2O)5Cl]2+ persist in solution. If
allowed to stand for several days, the solutions eventually do form the violet [Cr(H2O)6]3+
ion.

PROCEDURE

Copper(II) Complexes

Locate the bottles containing solid CuSO45H2O and CuCl22H2O.

Record your observations regarding the appearance of these two compounds. How can you
account for the difference in color of these two compounds?

o Add 0.50 mL (approximately 10 drops) of 0.10 M copper sulfate to each of four

small test tubes. Note the color of the solution.
o To one test tube, add a few drops of 15 M NH3.
o To the next test tube, carefully add 12 M HCl dropwise until the color change to a
yellow solution is complete.
o To the third, add 6M NaOH. An initial precipitate of Cu(OH)2 may form, which
redissolves in excess OH- to form [Cu(OH)4]2-.
o To the fourth test tube, add 5-10 drops of saturated NaNO2 solution.

In each case, record your observations and write the formula for the complex ion that is
formed.

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Iron(II) Complexes

o To a small test tube add 0.50 mL of water (approximately 10 drops) and a small
portion of solid ferrous sulfate. What color is solid ferrous sulfate? What color is the
resulting solution?

Iron(III) Complexes

o To small test tube add approximately 0.50 mL (approximately 10 drops) of 0.10 M of

Fe(NO3)3 solution. What color is the solution?
o To the test tube add a drop of KSCN solution. Note any changes in the color of the
solution.

Nickel(II) Complexes

o To each of two small test tubes add 0.50 mL (approximately 10 drops) of 0.10 M
Ni(NO3)2 solution.
o To the first, add a few drops of 15 M ammonia.
o To the second tube, add a solution of dimethylgloxime (DMG).
Record your observations.

Dimethylgloxime (DMG)

Cobalt(II) Complexes

o Add 0.50 mL (approximately 10 drops) of 0.10 M CoCl2 solution to each of two

small test tubes.
o To one test tube, 12M HCl dropwise until the color change appears complete.
o To the next test tube, add 10-15 drops of saturated KSCN solution. What do you
observe? Write the formulas for the complex ions that are formed.

Chromium(III) Complexes

o Locate container of CrCl36H2O.

o Obtain small test tubes and add 0.50 mL of water to the test tube.
o Add a very small portion of solid CrCl36H2O to the test tube. What do you
observe? What complex ions are responsible for the color in the test tube?

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Introduction to Coordination Chemistry Name:
Report Sheet 1

Copper(II)

What is the color of CuSO45H2O solution?

What is the color of CuCl22H2O solution?

Record your observations regarding the addition of reagent to a solution of aqueous

copper(II). In each case write a formula for the complex ion formed.

Reagent Added Complex Ion Formed Observation

15 M NH3

12 M HCl

6 M NaOH

NaNO2

Nickel(II)

What is the color of [Ni(H2O)6]2+ solution?

Record your observations regarding the addition of reagent to a solution of aqueous

nickel(II). In each case write a formula for the complex ion formed.

Reagent Added Complex Ion Formed Observation

15 M NH3

DMG

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Introduction to Coordination Chemistry Name:
Report Sheet 2

Iron(II)

What is the color of solid Fe(SO4).6H2O ?

Record your observations regarding the addition of reagent to a solid iron(II) salt and write
a formula for the complex ion formed

Reagent Added Complex Ion Formed Observation

H2O

Iron(III).

What is the color of Fe(NO3)3 solution?

Record your observations regarding the addition of reagent to a solution of aqueous

iron(III).

Reagent Added Complex Ion Formed Observation

KSCN

Cobalt(II)

What is the color of [Co(H2O)6]2+ solution?

Record your observations regarding the addition of reagent to a solution of aqueous

cobalt(II) and write a formula for the complex ion formed

Reagent Added Complex Ion Formed Observation

12 M HCl

KSCN

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 Introduction to Coordination Chemistry Name:
Report Sheet 3

Chromium(III)

What is the color of solid CrCl3.6H2O ?

Record your observations regarding the addition of reagent to a solid chromium(III) salt and
write a formula for the complex ion formed

Reagent Added Complex Ion Formed Observation

H2O