Question
In the polar aprotic solvent, the increasing order of nucleophilicity is:
CF3CH2O−, CH3CH2O−, CF3CH2S−, CH3CH2S−
A CF3CH2O < CH3CH2O−<CF3CH2S−<CH3CH2S−
B CF3CH2O−<CH3CH2O−<CF3CH2S−<CH3CH2S−
C CF3CH2O−<CH3CH2O−>CF3CH2S−<CH3CH2S−
D CF3CH2O−>CH3CH2O−>CF3CH2S−>CH3CH2S−
Solution
Correct option is B)
Oxygen is more electronegative than sulphur.
In the ethoxide ion, the negative charge is present on more electronegative O atom as
compared to S atom in ethyl sulphide ion.
Hence, the negative charge can be less readily donated by ethoxide ion than by ethyl
sulphide ion. Hence, ethyl sulphide ion is more nucleophilic than ethoxide ion.
Also when trifluoromethyl group is present, the nucleophilicity decreases due to the
electron-withdrawing effect of trifluoromethyl group.
Hence, option B is correct
1. Reminder: Nucleophilicity Is Measured By Reaction Rate
When discussing nucleophilicity we’re specifically talking about donating a pair
of electrons to an atom other than hydrogen (usually carbon). When a species
is donating a pair of electrons to a hydrogen (more specifically, a proton, H+)
we call it a base.
This post attempts to address one of the most vexing question to students of
organic chemistry. What are the factors that make a good nucleophile?
For our purposes, there are at least four key factors contributing
to nucleophilicity.
1. Charge
2. Electronegativity
3. Solvent
4. Steric hindrance
The first two should hopefully be familiar from the discussion of what makes
something a strong base. After all, basicity and nucleophilicity essentially
describe the same phenomenon, except basicity concerns donation of lone pairs
to hydrogen, and nucleophilicity concerns donations of lone pairs to all other
atoms. It’s the third and fourth points where extra factors come into play.
2. The Role Of Charge: Nucleophilicity Increases As An Atom’s Electron
Density Increases
Since a nucleophile is a species that is donating a pair of electrons, it’s
reasonable to expect that its ability to donate electrons will increase as it
becomes more electron rich, and decrease as it becomes more electron poor,
right? So as electron density increases, so does nucleophilicity.
A handy rule to remember for this purpose is the following: the conjugate
base is always a better nucleophile.
3. Electronegativity: Across The Periodic Table, Nucleophilicity Increases
With Decreasing Electronegativity
Assuming an atom has a pair of electrons to donate, the ability of a species to
donate that pair should be inversely proportional to how “tightly held” it is. The
key factor for determining how “tightly held” an electron pair is bound is the
familiar concept of electronegativity. Bottom line: as electronegativity
increases, nucleophilicity decreases. Note: It’s important to restrict application
of this trend to atoms in the same row of the periodic table; for instance, C N O
F, or Si P S Cl. Going down the periodic table, another factor comes into play
(next)
4. The Choice Of Solvent (Polar Protic vs. Polar Aprotic) Can Drastically
Affect Nucleophilicity Trends
Nucleophilicity is not a property inherent to a given species; it can be affected
by the medium it’s in (otherwise known as “the solvent”). [For an introduction
to the different classes of solvents, click here]
A polar protic solvent can participate in hydrogen bonding with a nucleophile,
creating a “shell” of solvent molecules around it like mobs of screaming teenage
fans swarming the Beatles in 1962. In so doing, the nucleophile is considerably
less reactive; everywhere it goes, its lone pairs of electrons are interacting with
the electron-poor hydrogen atoms of the solvent.
The ability of nucleophiles to participate in hydrogen bonding decreases as we
go down the periodic table. Hence fluoride is the strongest hydrogen bond
acceptor, and iodide is the weakest. This means that the lone pairs of iodide ion
will be considerably more “free” than those of fluoride, resulting in higher rates
(and greater nucleophilicity).
A polar aprotic solvent does not hydrogen bond to nucleophiles to a significant
extent, meaning that the nucleophiles have greater freedom in solution. Under
these conditions, nucleophilicity correlates well with basicity – and fluoride ion,
being the most unstable of the halide ions, reacts fastest with electrophiles.
[Often asked: why don’t we care about “non polar solvents” here? Remember
“like dissolves like”? If we want a reaction to take place, we need to use
solvents that will actually dissolve our nucleophile. Many nucleophiles are
charged species (“ions”) – they don’t dissolve in non-polar solvents.]
5. Nucleophilicity Decreases with Increasing Steric Hindrance
(“Bulkiness”)
Since, when discussing nucleophilicity, we’re often discussing reactions at
carbon, we have to take into account that orbitals at carbon that participate in
reactions are generally less accessible than protons are. An effect called “steric
hindrance” comes into play.
The bottom line here is that the bulkier a given nucleophile is, the slower the
rate of its reactions [and therefore the lower its nucleophilicity].
So comparing several deprotonated alcohols, in the sequence methanol –
ethanol – isopropanol – t-butanol, deprotonated methanol (“methoxide”) is the
strongest nucleophile, and deprotonated t-butanol (“t-butoxide”) is the poorest
(or “weakest”) nucleophile.
