INORGANIC REACTION

MECHANISM

Prepared by:
Ms.Sumina Ibrahim

07/05/2020
 Outline

Topics

 Redox Reaction
 Concept of oxidation-reduction with
examples
 Mechanism of redox reactions in
cordination compounds
o Inner Sphere Mechanism
o Outer Sphere Mechanism

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 Redox Reactions

• An oxidation-reduction (redox) reaction is a type of chemical

reaction that involves a transfer of electrons between two species.

• An oxidation-reduction reaction is any chemical reaction in which

the oxidation number of a molecule, atom, or ion changes by
gaining or losing an electron. Redox reactions are common and vital
to some of the basic functions of life, including photosynthesis,
respiration, combustion, and corrosion or rusting.

• Redox reactions are comprised of two parts, a reduced half and an

oxidized half, that always occur together. The reduced half gains
electrons and the oxidation number decreases, while the oxidized
half loses electrons and the oxidation number increases.

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 Examples of Redox Reactions
A few examples of redox reactions along with their oxidation and
reduction half-reactions are provided in this subsection.
• Example 1: Reaction Between Hydrogen and Fluorine
• In the reaction between hydrogen and fluorine, the hydrogen is
oxidized whereas the fluorine is reduced. The reaction can be
written as follows
H2 + F2 → 2HF
• The oxidation half-reaction is: H2 → 2H+ + 2e–
• The reduction half-reaction is: F2 + 2e– → 2F–
• The hydrogen and fluorine ions go on to combine in order to form
hydrogen fluoride.

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• Example 2: Reaction Between Zinc and Copper
This is a type of metal displacement reaction in which copper metal
is obtained when zinc displaces the Cu2+ion in the 
copper sulfate solution as shown in the reaction below.
Zn (s) + CuSO4 (aq) → ZnSO4 (aq) + Cu (s)
• The oxidation half-reaction can be written as: Zn → Zn2+ + 2e–
• The reduction half-reaction can be written as: Cu2+ + 2e– → Cu
• Example 3: Reaction between Iron and Hydrogen Peroxide
Fe2+ is oxidized to Fe3+ by hydrogen peroxide when an acid is
present. This reaction is provided below.
2Fe2+ + H2O2 + 2H+ → 2Fe3+ + 2H2O
• Oxidation half-reaction: Fe2+ → Fe3+ + e–
• Reduction half-reaction: H2O2 + 2e– → 2 OH–
• Thus, the hydroxide ion formed from the reduction of hydrogen
peroxide combines with the proton donated by the acidic medium to
form water.

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 Oxidizing and Reducing Agents
• The substance (atom, ion, and molecule) that gains electrons and is
thereby reduced to a low valency state is called Oxidising agent.
• The substance that loses electrons and is thereby oxidized to a
higher valency state is called a reducing agent.
 Important Oxidizing Agents
• Molecules made up of electronegative elements. Eg: O2, O3, and
X2 (halogens)
• Compounds containing an element which is in the higher oxidized
state. Eg: KMnO4, K2Cr2O7, HNO3, KClO3
• Oxides of metals and non-metals. Eg: MgO, CuO
• Fluorine is the strongest oxidizing agent.

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 Important Reducing Agents

• All metals, Eg: Na, Zn, Fe, Al

• A few non-metals Eg: C, Hydrogen, S, P
• Hydracids, Eg: HCl, HBr, HI, H2S
• Few compounds containing an element in the lower oxidation state,
Eg: FeCl2, FeSo4, SnCl2, Hg2Cl2
• Metallic hydrides, Eg: NaH, LiH, CaH2, etc..
• Organic compounds like HCOOH,
• Lithium is the strongest reducing agent in the solution and Cesium is
the strongest reducing agent in the absence of water. The
substances which act as oxidizing as well as reducing agents are
H2O2, SO2, H2SO3, HNO2, NaNO2

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Mechanism of redox reactions in
cordination Compounds

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 electron is transferred. Two basic paths appear to be possible, In
one, the electron effectively hops from one intact complex to the
other: this is called the outer- sphere mechanism. In the other
process, the oxidant and reductant are attached to each other by a
bridging molecule, atom, or ion through which the electron can pass:
this is called the inner-sphere mechanism.

• Inner-sphere mechanism
Inner sphere electron transfer or bonded electron transfer is a redox
 chemical reaction that proceeds via a covalent linkage—a strong
electronic interaction—between the oxidant and the reductant
reactants.

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 Some important points consider for inner sphere mechanism
 There should be a bridging ligand.
 One of the reacting substance should be labile.
 One of the reactant complex should be coordinatively unsaturated.

 Bridging Ligands:
• In coordination chemistry, a bridging ligand is a ligand that
connects two or more atoms, usually metal ions. The ligand may be
atomic or polyatomic. E.g. [CoCl(NH3)5]2+ 
 Labile
 A relatively unstable and transient chemical species or (less
commonly) a relatively stable but reactive species. E.g. [Cr(OH2)6]2+
 Unsaturated complex
 A transition metal complex that possesses fewer ligand
 than exist in the coordinative saturated complex. These complexes
usually have fewer than 18 outer shell electrons at the central metal
atom. E.g. [Cr(OH2)5]2+,
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EXPLANATION (INNER SPHERE MECHANISM)

[CoCl(NH3)5]2+ + [Cr(OH2)6]2+ [(NH3)5Co-Cl-Cr(OH2)5]4+

[Co(OH2)6]2+ + [CoCl(OH2)5]2+ 

When [CoCl(NH3)5]2+ is reduced by [Cr(OH2)5]2+, an intermediate complex,

[(NH3)5Co-Cl-Cr(OH2)5]4+, is formed in which the chlorine atom forms a
bridge between cobalt and chromium. As a result of an electron transfer
from chromium to cobalt through chlorine, [Co(NH3)5Cl]+ , in which cobalt
is reduced from a trivalent to a divalent oxidation state and [Cr(OH2)6]3+, in
which chromium is oxidized from a divalent to a trivalent oxidation state,
are formed. This kind of reaction is a redox reaction via the inner-sphere
mechanism. The anions other than halogens suitable for such bridge
formation are SCN-, N3-, CN-, etc.

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It was observed that in the reduction of [CoCl(NH3)5]2+ is reduced by
Chromium (II), the chromium (III) product always contained a chloride
ion. The complex [CoCl(NH3)5]2+ containing radioactive chloride ion
which is dissolved in a solution containing chromium (II) and
unlabelled chloride ion. After reduction which was very rapid, the
product of chromium complex only contained the labeled radioactive
chloride ions. This proved that the CoCl(NH3)5]2+ is the only source to
provide the chloride ion to the chromium complex.

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Once the electron is transferred from chromium (II) to cobalt (III), the
chromium (III) formed attracts the chloride more strongly than does
the cobalt (II), and therefore chloride become the part of chromium
(III) complex.

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