There are several techniques for synthesizing coordination compounds, including:
1) Reacting a metal salt with a ligand.
2) Ligand replacement reactions, where one ligand is replaced by another.
3) Oxidation-reduction reactions, by reducing or oxidizing a metal compound in the presence of a ligand.
4) Reactions of two metal compounds.
There are several techniques for synthesizing coordination compounds, including:
1) Reacting a metal salt with a ligand.
2) Ligand replacement reactions, where one ligand is replaced by another.
3) Oxidation-reduction reactions, by reducing or oxidizing a metal compound in the presence of a ligand.
4) Reactions of two metal compounds.
There are several techniques for synthesizing coordination compounds, including:
1) Reacting a metal salt with a ligand.
2) Ligand replacement reactions, where one ligand is replaced by another.
3) Oxidation-reduction reactions, by reducing or oxidizing a metal compound in the presence of a ligand.
4) Reactions of two metal compounds.
There are several techniques for synthesizing coordination compounds, including:
1) Reacting a metal salt with a ligand.
2) Ligand replacement reactions, where one ligand is replaced by another.
3) Oxidation-reduction reactions, by reducing or oxidizing a metal compound in the presence of a ligand.
4) Reactions of two metal compounds.
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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.
