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Chapter 27: Problem 5

(a) What are nucleophilic substitution reactions in coordination compounds? (b) Discuss the dissociative and association mechanism for octahedral complexes.

Short Answer

Expert verified
Nucleophilic substitution reactions in coordination compounds are where a nucleophile replaces a ligand in the coordination sphere of a metal ion. The dissociative mechanism involves the removal of a ligand first then addition of the nucleophile, while an associative mechanism involves the addition of a nucleophile first then departure of a ligand from an octahedral complex.

Step by step solution

01

Understanding Nucleophilic Substitution Reactions

Nucleophilic substitution reactions in coordination compounds are those where a nucleophile (which is an electron-rich species) replaces a ligand in the coordination sphere of a central metal ion.
02

Explaining Dissociative Mechanism

Dissociative mechanism in octahedral complexes involves the removal or dissociation of a ligand from the complex ion before the addition of the incoming nucleophile. This results in the formation of an unstable intermediate with coordination number less than 6, usually 5, which is why this mechanism is also known as the 'D mechanism'.
03

Explaining Associative Mechanism

On the other hand, associative mechanism involves the addition of an incoming nucleophile to an octahedral complex ion before the departure of a ligand. The complex ion initially forms an unstable intermediate with coordination number more than 6, usually 7. Then a ligand leaves, resulting in the substitution product. This mechanism is also known as the 'A mechanism'.

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Most popular questions from this chapter

Differentiate between outer-sphere mechanism and inner-sphere meachanism for electron- transfer reactions.

Differentiate between \(\mathrm{S}_{\mathrm{N}^{1}}\) mechanism and \(\mathrm{S}_{\mathrm{N}^{1}} \mathrm{CB}\) mechanism with the help of suitable examples.

Discuss the factors responsible for the acid hydrolysis of octahedral complexs.

Account for the following: (a) \(\left[\mathrm{Pt}\left(\mathrm{NH}_{3}\right)_{4}\right]^{2+}\) gives trans \(\left[\mathrm{Pt}\left(\mathrm{NH}_{3}\right)_{2} \mathrm{Cl}_{2}\right]\) with \(\mathrm{Cl}^{-}\) while \(\left[\mathrm{PtCl}_{4}\right]^{2-}\) on treatment with \(\mathrm{NH}_{3}\) gives cis \(\left[\mathrm{Pt}\left(\mathrm{NH}_{3}\right)_{2} \mathrm{Cl}_{2}\right]\) (b) \(\left[\mathrm{Cr}\left(\mathrm{H}_{2} \mathrm{O}\right)\right]^{3+}\) is inert but \(\left[\mathrm{Cr}\left(\mathrm{H}_{2} \mathrm{O}\right)_{6}\right]^{2+}\) is labile towards ligand substitution reactions.

Discuss the concept of lability on the basis of valence bond theory and crystal-field theory with the help of suitable examples.
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