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Why is $\ce{RS-}$ (a thiolate) more nucleophilic than $\ce{RO-}$(an alkoxide)?

According to my logic, the larger size of the sulfur atom will allow the negative charge to be dispersed more as compared to the negative charge on the oxygen atom. Thus, shouldn't $\ce{RS-}$ be less nucleophilic as compared to $\ce{RO-}$ ion?

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  • $\begingroup$ $\ce{S-}$ is quite bigger in size hence it shows lesser hydrogen bonding in protic solvents hence they are better nucleophiles in protic solvents. But when we take polar aprotic solvents, no hydrogen bonding is possible so, nucleophilicity $\propto$ basicity and your argument becomes valid. $\endgroup$
    – Sujith Sizon
    Commented Jan 1, 2016 at 12:57
  • $\begingroup$ It depends entirely on the solvent that the reaction is being conducted in. If the solvent is polar protic, the thiolate anion is more nucleophilic because of polarizability factors. Whereas if the solvent is polar aprotic basicity takes precedence as the gauge for nucleophilicity. $\endgroup$
    – Anonymous
    Commented Nov 7, 2022 at 0:05

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It's true that thiolate ion is more nucleophilic than alkoxide ion. You are going in a right way. The order of nucleophilities is according to polarisability of atom. As we know, the size of atoms goes on increasing down the group.

atomic size: $\ce{S>O}$

Due to increase in size of atoms, the electrons are more loosely bound to nucleus. Hence, the atoms are now easy polarise. As a result, electrons are easily polarisable down a group.

Thus, $\ce{RS-}$ of thiolate ion is more polarisable than $\ce{RO-}$ of alkoxide ion. Therefore, thiolate ion is more nucleophilic than alkoxide ion.

The polarisability of nucleophile is more important in case of nucleophilic substitution reaction where the nucleophile electrons are polarised by the positive charge of electrophile and bond is formed during the reaction.

As nucleophilicity is a kinetic factor. More stronger the nucleophile, greater is its rate constant. The following is relative rate constant of both nucleophile on reaction with iodomethane by using methanol as reference whose rate constant is taken as unity:

$\ce{CH3-O-};~k = 2\cdot 10^6$

$\ce{CH3-S-};~k = 1\cdot 10^9$

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  • $\begingroup$ Hmmm.... does that mean thiolate ions are more basic than alkoxide ions? $\endgroup$
    – Gummy bears
    Commented Jan 1, 2016 at 16:21
  • $\begingroup$ no.. there is not always that basicity parallels nucleophilicity. Though Here, alkoxide ion is more basic than thiolate ion. $\endgroup$
    – solanki...
    Commented Jan 1, 2016 at 16:24
  • $\begingroup$ And why is that? I don't get the logic behind it. :( $\endgroup$
    – Gummy bears
    Commented Jan 2, 2016 at 3:56

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