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Q.

Consider thiol anion RSΘ and alkoxy anion ROΘ.

Which of the following statements is correct?

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a

RSΘ is less basic and less nucleophilic than ROΘ

b

RSΘ is less basic but more nucleophilic than ROΘ

c

RSΘ is more basic and more nucleophilic than ROΘ

d

RSΘ is more basic but less nucleophilic than ROΘ

answer is B.

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Detailed Solution

Nucleophilic strength depends on the electronegativity of the atom. Lower the electronegativity of an atom, larger the nucleophilic strength of an atom and more readily it will donate electrons to the electrophilic (edeficient) species. Since, electronegativity decreases down the group, thus
nucleophilic strength increases down the group. Hence, RS is more nucleophilic than RO due to less electronegativity of S than O. On the other hand, basic strength of an atom depends upon the tendency to accept a proton more readily. Since, OH bond is longer than SH bond, thus RO has a greater tendency to accept a proton than RS

Thus, basic strength of the central atom decreases down the group.
Hence, RS is more nucleophilic but less basic than RO.

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