Steric Effects in Lewis Basicity: F-Strain

▪ In general, steric effects only slightly influence ion-transfer equilibria in proton

transfer reactions. In Lewis acid-base reactions, steric effects may be quite large.

▪ Example: Whereas 2-methylpyridine is a stronger base toward a proton than

pyridine (as expected from inductive effect of -CH3 group), it is a much weaker base
than pyridine towards Lewis acid such as BMe3. Shifting the methyl group to the meta
position slightly increase the basicity. BMe3 does not react at all with 2,6-dimethyl
pyridine (2,6-lutidine).

ΔH (kJ/mole): -71 -42 -74

Reaction with BMe3: stable unstable stable no reaction

▪ Explanation: All these observations can be explained by the steric interactions

between the substituents on the acids and bases which appear “in front” during
adduct formation. Such strain is termed as front-strain or F-strain. Such strain is
lowered when the acid and base can form adduct from a larger distance.

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 Steric Effects in Lewis Acidity: B-Strain
▪ A similar effect like F-strain occurs due to change in geometry of the central atom
on adduct formation. When a B atom changes from trigonal planar to pyramidal
orientation of its valence orbitals, the substituents comes closer. If the substituents
are branched, they will introduce steric hindrance in the adduct. This is termed as
back-strain or B-strain, since the crowding groups are on back side of acceptor sites.

▪ Example: B(Me)3 (Me = -CH3) forms a stronger adduct with NH3 than B(iPr)3 (iPr =
iC H = isopropyl).
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▪ Trimesitylboron (B(Mes)3; Mes = mesityl) is inert even to stronger bases such as

methoxide (OMe-) ion because crowding of the mesityl groups prevents change of
geometry of the boron atom from trigonal planar to pyramidal.

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 Hard and Soft Acids and Bases
Experimental Determination

▪ Soft and hard acids are identified empirically by the opposite order of strengths (as
measured by the equilibrium constant, Kf, for the formation of the complex) with
which they form complexes with halide ion bases:

▪ Hard acids bond in the order:

I- < Br- < Cl- < F-
R3P < R3N
R2S < R2O

▪ Soft acids bond in the order:

I- > Br- > Cl- > F-
R3P > R3N
R2S > R2O

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Hard and Soft Acids and Bases
Experimental Determination

▪ From F- to I-:

▪ Steep downward slope: hard acids (Al3+, Sc3+, In3+)

▪ Steep upward slope: soft acids (Hg2+, Pd2+, Cd2+)

▪ Less steep downward slope: borderline hard acids

(Zn2+, Cu2+)

▪ Less steep upward slope: borderline soft acid (Pb2+)

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 HSAB Principle
▪ Hard Acid: A Lewis acid with an acceptor centre of low polarizability, high positive
charge, small size.

▪ For hard acids, binding strength increases as the electrostatic parameter (ξ = z2/r) of
the anion increases. They tend to form complexes (with hard bases) in which simple
electrostatic or ionic interactions are dominant.

▪ Soft Acid: A Lewis acid with an acceptor centre of high polarizability, low positive
charge, large size.

▪ For soft acids, binding strength increases with increasing polarizability of the anion.
They tend to form complexes (with soft bases) in which covalent bonding is important.

▪ Hard Base: A Lewis base with a donor centre of low polarizability, high electron
negativity, small size, no low energy empty d-orbitals.

▪ Halides and oxoanions are classified as hard because ionic bonding is predominant
in most of the complexes they form.
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 HSAB Principle
▪ Soft Base: A Lewis base with a donor centre of high polarizability, low electron
negativity, large size, low energy empty d orbitals

▪ Many soft bases bond through a carbon atom, such as CO or CN–. In addition to
donating electron density to the metal through a σ interaction, these small multiply
bonded ligands are able to accept electron density through the low-lying empty π
orbitals (LUMO). So, the bonding is predominantly covalent in character.

▪ HSAB Principle: Hard (Lewis) acids prefer to bind to hard (Lewis) bases
Soft (Lewis) acids prefer to bind to soft (Lewis) bases
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