Why chelate compounds are stable than nonchelated compounds?

1 Answer
Dec 3, 2016

Well, to compare them on equal footing, we would be considering the same bonds being made with each kind of compound.

Consider the following reaction:

#["M"("NH"_3)_6]^(z+) + 3(en) rightleftharpoons ["M"(en)_3]^(z+) + 6"NH"_3#

where #en# is ethylenediamine:

http://www.sigmaaldrich.com/

Visually, at first glance, the only difference between #en# and #"NH"_3# is that #en# has a #-"CH"_2-"CH"_2-# bridge connecting the two nitrogens, and that both "teeth" on #bb(en)# bind to the same metal.

(They both have the same atoms that bind, and they both contribute zero charge.)

This will therefore have a net zero enthalpy for the breaking and formation of the six #"M"-"N"# interactions, because each of the six #"NH"_3#'s would form one #"M"-"N"# interaction, but each of the three #en#'s would form two #"M"-"N"# interactions.

All that means is that enthalpy is not a significant stabilizing factor.

The main difference we're looking for is that #en# is fixed to a cis configuration, so by binding via two "teeth", it is going to restrict its own mobility.

Entropy is smaller with more restricted motion.

https://figures.boundless-cdn.com/

Therefore, its entropy of bond formation is less positive, and the decrease in entropy due to the interaction corresponds to favoring #en# over #"NH"_3# (since #DeltaS_"rxn" = sum DeltaS_"bonds broken" - sum DeltaS_"bonds formed"#).

We call this the chelate effect, where the binding of a chelating ligand like #en# in comparison to #NH_3# is entropically favorable. Hence, a chelating ligand creates a more entropically stable compound.