Synthesis of Coordination Compounds

SYNTHESIS OF COORDINATION
COMPOUNDS
 Zeise’s salt, K[Pt(C2H4)Cl3], dates from the early 1800s, and
Werner’s classic syntheses of cobalt complexes were described

over a century ago.
 Synthetic techniques used to prepare coordination compounds
range from simply mixing the reactants to employing

nonaqueous solvent chemistry.
Reaction of a Metal Salt with a Ligand
 One of the techniques for producing coordination
compounds is to simply combine the reactants.

Some reactions of this type are the following:
Ligand Replacement Reactions
 The replacement of one ligand by another is the most
common type of reaction of coordination compounds,

and the number of reactions of this type is enormous.
 Some are carried out in aqueous solutions, some in
nonaqueous media, and others can be carried out in the

gas phase.
 One such reaction is:

 Replacement reactions are important because frequently one type
of complex is easily prepared and then can be converted to another

that cannot be obtained easily.
 Gaseous butadiene will react with an aqueous solution of K2[PtCl4]
to give a bridged complex in which Cl- ligands are displaced.
 A large number of syntheses involve replacement reactions.

Oxidation-Reduction Reactions
 Many coordination compounds can be prepared when a
compound of the metal is either reduced or oxidized in the

presence of a ligand.
 An interesting reaction of this type involves the reduction of
dichromate by oxalic acid as shown by the following

equation:
 In other reactions, the metal may be oxidized as the complex is
formed.
 Numerous complexes of Co(III) have been prepared by the
oxidation of solutions containing Co(II).
 This technique is particularly useful in the case of cobalt because
Co3+ is a strong oxidizing agent that reacts with water if it is not

stabilized by complexation.
 Consider the following reaction:
 Heating the product of the second reaction yields trans-
[Co(en)2Cl2]Cl by the loss of HCl.
 Dissolving trans-[Co(en)2Cl2]Cl in water and evaporating the
solution by heating results in the formation of cis- [Co(en)2Cl2]Cl

as the result of an isomerization reaction.
Reaction of Two Metal Compounds
 Several synthetic processes involve the reaction of two

metal salts.
 A well-known example of this type is the following.
Precipitation Making Use of the Hard-Soft
Interaction Principle
 As a consequence of the hard-soft interaction principle, ions of
similar size and magnitude of charge interact best.
 That interaction includes the formation of precipitates.
 It is possible to make use of this principle when isolating
complex ions that are relatively unstable.
 A well-known case of this type is the isolation of the
[Ni(CN)5]3- ion, which results when aqueous solutions

containing Ni2+ also contain an excess of CN-.
 Attempts to isolate [Ni(CN)5]3- by adding K+ were not successful
because what was obtained was K2[Ni(CN)4] and KCN.
 It was only when a large cation having a +3 charge was utilized
that the pentacyanonickelate (II) ion was obtained in a solid

product.
 The large +3 cation used was [Cr(en)3]3-. With that cation, the
solid product was [Cr(en)3][Ni(CN)5].

 The following equations describe the process:
Reactions of Metal Compounds with Amine Salts
 These compounds contain a cation that is a protonated amine

that can function as a proton donor.
 Consequently, the molten salts are acidic and they undergo
many reactions in which they function as acids.
 This behavior is also characteristic of ammonium chloride as
well as pyridine hydrochloride (or pyridinium chloride).
 Numerous metal oxides and carbonates react readily with the
molten amine salts, as illustrated by the following equation:
REACTIVATES OF COORDINATION COMPOUNDS
Acid-catalyzed reactions of complexes:

 As in many areas of chemistry, there are reactions of
coordination compounds that are not what they appear.
 For example,
the reaction appears to be a substitution reaction in which H2O

replaces F-.
 However, this reaction has a rate that is strongly pH dependent,
suggesting that the reaction does not follow the usual pattern for
complexes of Co3+.
 The fact that H+ is involved suggests that the reaction does not
proceed by a dissociative pathway.
 Instead, the reaction is believed to proceed as follows:

 In the first step, the reaction produces the conjugate acid of
the complex by protonation of a coordinated F- ion.
 That conjugate acid then undergoes substitution in a
dissociative pathway.
 Acid catalysis is observed most often in reactions of

complexes containing ligands that are basic (so they can
accept protons) or ligands that can form hydrogen bonds.
Electron transfer reactions
 An aqueous solution containing complexes of two different
metal ions may make it possible for a redox reaction to occur.
 In such cases, electrons are transferred from the metal ion
being oxidized to the metal ion being reduced.
 For example,
In this reaction, an electron is transferred from Cr2+ to Fe3+, and

such reactions are usually called electron transfer or electron
exchange reactions.
 Electron transfer reactions may also occur in cases where only
one type of metal ion is involved. For example, the reaction
represents an electron transfer from [*Fe(CN)6]4- (where *Fe is a

different isotope of iron) to Fe3+ in [Fe(CN)6]3-.
 This is an electron transfer in which the product differs from the
reactants only in that a different isotope of Fe is contained in the
+2 and +3 oxidation states.

Synthesis of Coordination Compounds

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SYNTHESIS OF COORDINATION

Werner’s classic syntheses of cobalt complexes were described

 Synthetic techniques used to prepare coordination compounds

range from simply mixing the reactants to employing

compounds is to simply combine the reactants.

 The replacement of one ligand by another is the most

common type of reaction of coordination compounds,

 Some are carried out in aqueous solutions, some in

nonaqueous media, and others can be carried out in the

 One such reaction is:

of complex is easily prepared and then can be converted to another

 Gaseous butadiene will react with an aqueous solution of K2[PtCl4]

to give a bridged complex in which Cl- ligands are displaced.

 A large number of syntheses involve replacement reactions.

 Many coordination compounds can be prepared when a

compound of the metal is either reduced or oxidized in the

 An interesting reaction of this type involves the reduction of

dichromate by oxalic acid as shown by the following

 Numerous complexes of Co(III) have been prepared by the

oxidation of solutions containing Co(II).

 This technique is particularly useful in the case of cobalt because

Co3+ is a strong oxidizing agent that reacts with water if it is not

 Heating the product of the second reaction yields trans-

[Co(en)2Cl2]Cl by the loss of HCl.

 Dissolving trans-[Co(en)2Cl2]Cl in water and evaporating the

solution by heating results in the formation of cis- [Co(en)2Cl2]Cl

 Several synthetic processes involve the reaction of two

 As a consequence of the hard-soft interaction principle, ions of

similar size and magnitude of charge interact best.

 That interaction includes the formation of precipitates.

 It is possible to make use of this principle when isolating

complex ions that are relatively unstable.

 A well-known case of this type is the isolation of the

[Ni(CN)5]3- ion, which results when aqueous solutions

because what was obtained was K2[Ni(CN)4] and KCN.

 It was only when a large cation having a +3 charge was utilized

that the pentacyanonickelate (II) ion was obtained in a solid

solid product was [Cr(en)3][Ni(CN)5].

 These compounds contain a cation that is a protonated amine

Acid-catalyzed reactions of complexes:

coordination compounds that are not what they appear.

the reaction appears to be a substitution reaction in which H2O

proceed by a dissociative pathway.

 Instead, the reaction is believed to proceed as follows:

 Acid catalysis is observed most often in reactions of

metal ions may make it possible for a redox reaction to occur.

 In such cases, electrons are transferred from the metal ion

being oxidized to the metal ion being reduced.

In this reaction, an electron is transferred from Cr2+ to Fe3+, and

represents an electron transfer from [*Fe(CN)6]4- (where *Fe is a

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represents an electron transfer from [Fe(CN)6]4- (where Fe is a