Transition Metals part 3

We are now going to look at the reactions (and colours) of complex ions. There are two main reactions:
ligand substitution (exchange) and deprotonation.

Ligand Substitution

In a ligand exchange reaction, you simply swap one or more ligands in a complex ion for something else.

You can get complete or partial substitution.

Complete substitution:

Monodentate ligands

[Fe(H2O)6]2+ + 6NH3 [Fe(NH3)6]2+ + 6H2O

All we have done is swap all the waters for all the ammonias. Both are neutral ligands so the overall
charge doesnt change.

Cu(H2O)6]2+ + 4Cl- [CuCl4]2- + 6H2O

In this example we are adding chloro ligands to an octahedral complex. Cl- is provided by HCl usually.

We mentioned in the previous part of the tutorial that you can only fit four chloro atoms around a metal
due to their greater size. This means that there is a change in shape to tetrahedral.

This is still complete substitution, as all the waters have been removed, even although we have only
added four chloro atoms.

Also note the change in charge on the complex. On the left hand side the water molecules are neutral so
the 2+ must come from the copper.

Multi or bidentate ligands

[Cu(H2O)6]2+ + EDTA4- [Cu(EDTA)]2+ + 6H2O

The above example is very common. We only need one EDTA molecule to replace all 6 H2O molecules.
This means there is an increase in entropy and the resulting EDTA complex is very stable.

when you swap a monodentate ligand for a bidentate or multidentate, the complex formed is more
stable than the original complex. This is due to an increase in entropy.

Count up the moles on each side of the equation. There are 2 moles on the left side and 7 moles on
the right side. This is the entropy of the system as seen in Topic 13. The increase in moles = an
increase in entropy. You can also say that the equilibrium lies further to the right now.
Partial substitution:

We are starting with an octahedral complex of six waters.

But only four of the waters have been exchanged as we are only adding four ammonias:

[Cu(H2O)6]2+ + 4NH3 [Cu(NH3)4(H2O)2]2+ + 4H2O

Students get confused with partial substitution, as they are not sure what complex is formed. It seems
like any number of ligands could be exchanged.

But in the example above, we are told that four ammonias are added so that makes it easy. Just swap
four ammonias for four waters and keep the remaining two waters in their original place. The complex is
still octahedral.

the question should make it obvious how many ligands are being exchanged. Either that or you
should know the different complexes (see the tables below and in part 4).

Deprotonation reactions
H2O as a base

You can add H2O as a base to a complex ion fan acidic solution. As we are forming H3O+, an acidic
solution is formed.

[Cu(H2O)6]2+ + H2O [Cu(H2O)5(OH)]+ + H3O+

A base is a proton acceptor, which means it removes H+ ions.

H2O
H+
H2O H2O OH
H2O OH2 OH2 Cu2+
Cu2+ H2O
H2O OH2
OH2
H2O H2O
+ H3O+

Complex ion reactions and colours

This next part of the topic relies heavily upon the table below and features the two reactions we looked
at above.

If you can understand what is going on here, write out equations or each reaction and know the colours
then youve cracked it.
The 5 main ions looked at are Fe2+, Fe3+, Cu2+, Cr3+ and Co2+

we will look at this table in depth below. Remember the two main reactions: deprotonation and
ligand substitution/exchange. There is no redox going on here.

Complex a few drops NaOH(aq) or excess NaOH(aq) excess NH3(aq)

NH3(aq)
[Cr(H2O)6]3+ Pale green ppt ppt dissolves deep green ppt dissolves green
green Cr(H2O)3(OH)3 soln. solution
[Cr(OH)6]3- [Cr(NH3)6]3+
[Co(H2O)6]2+ Blue ppt No reaction ppt dissolves Brown
pink Co(H2O)4(OH)2 solution [Co(NH3)6]2+
[Fe(H2O)6]2+ Dirty green ppt No reaction No reaction
pale green Fe(H2O)4(OH)2
[Fe(H2O)6]3+ Red-brown ppt No reaction No reaction
yellow Fe(H2O)3(OH)3
[Cu(H2O)6]2+ Pale blue ppt No reaction ppt dissolves deep
blue Cu(H2O)4(OH)2 blue soln.
[Cu(NH3)4(H2O)2]2+

Reaction 1: precipitate formation (a few drops of base)

the starting point for all these reactions is the metal ion with 6 water ligands around it.

We are now going to look at reactions that involve adding a base to complex ions. The base is either NH3
or NaOH.

when a small amount of base is added to a complex ion, a precipitate (a solid) forms

To form the precipitate the complex must lose the charge and become neutral. When the complex is
neutral, it no longer stays in solution and a precipitate forms. This is deprotonation.

Example

[Cr(H2O)6]3+ + 3OH- Cr(H2O)3(OH)3(s) + 3H2O

We have formed the precipitate Cr(H2O)3(OH)3 or you can simply write it as Cr(OH)3 if you prefer.

Alternatively if we add NH3 as the base:

[Cr(H2O)6]3+ + 3NH3 Cr(H2O)3(OH)3(s) + 3NH4+

We get the same precipitate. The only difference is the NH4+ formed instead of H2O.

To go from 3+ to neutral we need to remove 3 x H+.

Reaction 2: redissolving the precipitate

we will still use NaOH and NH3 as the bases but now there is a difference in how they react. The point
is to try to redissolve the precipitate formed.

adding excess NaOH is further deprotonation. Adding excess NH3 results in ligand substitution

Adding excess NaOH

The good news is, only the Cr precipitate reacts, so there is not much to remember.

Cr(H2O)3(OH)3 + 3OH- [Cr(OH)6]3- + 3H2O

Cr(H2O)3(OH)3 is said to be amphoteric i.e. reacts with acid or base. The other precipitates in the
above table do not redissolve with NaOH.

to go from the precipitate back to the original complex can be done by adding acid. All the
precipitates do this reaction e.g.

Cu(H2O)4(OH)2 + 2H+ [Cu(H2O)6]2+

Adding excess NH3

When adding ammonia to a precipitate, if it redissolves, then it is just a ligand substitution:

Cr(H2O)3(OH)3 + 6NH3 [Cr(NH3)6]3+ + 6H2O

watch out for the Cu complex formed as it only does partial substitution.

Addition of HCl
The point of adding HCl is to provide Cl- ions/ligands. You need to know about Cu and Co complexes
involving Cl- ligands.
Cu
[Cu(H2O)6]2+ + 4Cl- [CuCl4]2- + 6H2O

Cu complex formed is yellow/green

Co
[Co(H2O)6]2+ + 4Cl- [CoCl4]2- + 6H2O

Co complex formed is blue

Chromium

all the above reactions did not involve redox. These reactions do involve redox.

Cr exists as Cr2+, Cr3+, CrO42- and Cr2O72-

CrO42- and Cr2O72- are both 6+.

The diagram below shows the conversion between each of the ions. Zn is used as a reducing agent and
H2O2 or air is the oxidising agent.

H+

Cr2O72- CrO42-
OH-
H2O2/OH- Zn

Cr3+

Air Zn

Cr2+
 the chromium colours in this diagram are not listed in the specification but I put them in anyway as
they used to get asked all the time.

Ionic equations

2CrO42- + 2H+ Cr2O72- + H 2O

or
Cr2O72- + 2OH- 2CrO42- + H2O

note that there are no electrons involved as it is not redox

Vanadium

Ion Colour

V2+ purple

V3+ green

V4+ (VO2+) blue

V5+ (VO2+) yellow

vanadium colours are required. The questions are just normal transition metal or redox potential
style.