Chapter 27: Problem 18

Discuss the inner-sphere mechanism for electron transfer reaction with the help of a suitable example.

Short Answer

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Inner-sphere electron transfer happens through a mutual ligand that creates a bridge between the reactants. In the hexaaquachromium(III) and hexacyanoferrate(II) reaction, a cyanide ligand forms a bridge where an electron is transferred, changing the oxidation states of iron and chromium.

Step by step solution

Concept Background

The inner-sphere mechanism is a type of electron transfer where the reaction proceeds through a transient intermediate in which the two reacting species are linked by a mutual ligand. This intermediate is often called a 'bridged complex'.

Providing Example of Inner-sphere Mechanism

A classic example of an inner-sphere mechanism is the reaction between hexaaquachromium(III) and hexacyanoferrate(II). The reaction can be represented as follows: \( [Cr(H_2O)_6]^{3+} + [Fe(CN)_6]^{4-} -> [Cr(H_2O)_5-OH]^{2+} + [Fe(CN)_6]^{3-} \)

Explaining the Mechanism

In the mechanism, the first step involves replacement of a water molecule in the hexaaquachromium(III) by a cyanide ligand from the hexacyanoferrate(II), forming a bridge. This results in the transient intermediate \( [Cr(H_2O)_5-CN-Fe(CN)_5]^{2-} \). In the second step, electron transfer happens across the bridge from \( Fe^{2+} \) to \( Cr^{3+} \), changing their oxidation states. Finally, the cyanide bridge breaks, giving the products \( [Cr(H_2O)_5-OH]^{2+} \) and \( [Fe(CN)_6]^{3-} \)

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Discuss the inner-sphere mechanism for electron transfer reaction with the help of a suitable example.

Short Answer

Step by step solution

Concept Background

Providing Example of Inner-sphere Mechanism

Explaining the Mechanism

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