Laboratory 9: Preparation and Characterization

of a Metal-Ligand Complex
Many of the compounds that inorganic chemists study are those of the d-block of the
periodic table, or the transition metals. One very important aspect of the chemistry of
the transition metals is the fact that they are able to form coordination complexes with
many common molecules and ions, such as water, chloride,
L
ammonia, which we call ligands (see figure to the right). These
compounds form because the metals have empty valence orbitals
that may accept lone pairs of electrons and the ligands have one
L
L
or more lone-pairs of electrons to share. A coordination complex,
M
therefore, is a molecule or ion containing a central metal, M, that is
L
L
chemically bound to one or more ligands, L.

L
The special type of bond in a metal-ligand complex, in which both
electrons are donated by the ligands, is called a dative or
coordinate covalent bond. A metal that accepts a lone pair of electrons from a
ligand is said to be a Lewis acid, while an electron pair donor (a ligand such as water,
chloride, etc.) is said to be a Lewis base. Studies of coordination complexes give
inorganic chemists broader understanding of a wide variety of chemical phenomena,
ranging from the functioning of enzymes that contain metal ions to the working of
industrial catalysts.
In this experiment you and your partners will synthesize four
O
O
coordination compounds using the ligand acetylacetone
C
C
(Hacac), the structure of which is shown to the right. There is
CH3
C
H
C
3
another important for of this
H2
compound, called a tautomer, in
OH
O
which the a proton moves from the central carbon to one of
the oxygen atoms (Notethis is not a resonance structure as
C
C
it involves more than the movement of electrons). Although
C
H
H3C
C
3
H
this second form (see figure to the left) is present at only a
small concentration, it is the form that binds to the metals.
In order for the ligand to react with
a metal, a proton must be
removed from the central carbon.
This is easily accomplished by the
addition of some base to the
reaction. The removal of one H+
will leave the ligand with an
overall charge of 1 as shown to
the right.

H3 C

H3 C
C

OH
+ base

HC
C
H3 C

+ Hbase

HC

C
H 3C

Typically, two or three acac ligands are required to form a metal complex. In the case
of chromium(III), for example, three ligands form the metalligand complex shown to the right. In this drawing, a line
formula is used to abbreviate the structure representing the
O
ligands carbon backbone. The oxygen atoms form an
O
O
octahedral arrangement around the chromium atom. The
Cr
charge on the metal is +3 and each of the ligands has a
O
O
charge of 1; the complex, therefore has an overall charge
O
of 0.
For obvious reasons, chemists have adopted shorthand
names for metal complexes and their ligands. The ligand is abbreviated acac after its
common name acetylacetonate. The metal complex is abbreviated Cr(acac)3. Since
the product is neutral and has organic shrubbery on the outside, it insoluble in water
and precipitates from solution once it forms. This is a tremendous benefit because it
enables us to readily recover the products from the aqueous reaction mixture.
Pre-Lab Assignment
There is no pre-lab assignment this week.

Experimental Procedure
As a group, you will need to prepare each of the M(acac)3 complexes described below.
In addition to preparing them, you will also find a way to recrystallize the compounds
and youll characterize each them spectroscopically using IR and UV/Vis spectroscopy.
You should complete the syntheses during the first week; during the second week you
will complete the recrystallizations and spectroscopic characterizations.
NOTE: Reactions that require heating acetylacetone must be done in the hood!

I. Syntheses
A. Preparation of Co(acac)3.1
Add approximately 1.0 g of powdered Co(II) carbonate into a 50-mL Erlenmeyer flask
and add 8 mL of acetylacetone. Drop in a small magnetic stir bar and cover with a
small watch glass. Place the reaction vessel into a water bath on a stirring hot plate
(Notedo not set the flask directly on the bottom of the water bath; instead, clamp it so
that the flask is suspended within the water bath with its contents below the water line;
refill the bath as needed as the water boils off during heating).
Stir the reaction using the magnetic stirring bar and heat the reaction to about 80C ,
maintaining it at this temperature for approximately 5 minutes. Slowly add 6 mL of 10%

hydrogen peroxide (H2O2) drop-wise at a rate of 1-2 mL/min using a disposable pipette
while continuing to stir the reaction mixture. CAUTION: 10% H2O2 will damage the
surface of the skin! Wear gloves or be extra careful! You can leave the reaction on
the hot plate during this time, but make sure you add the hydrogen peroxide slowly and
keep a close watch on your solution. The reaction will bubble vigorously, and you dont
want it to boil over!
Reheat the mixture to 80C after the addition of H2O2 is complete, then add an
additional 6 mL of H2O2 in the same manner. After the second addition of H2O2 is
complete, remove the water bath, place the flask directly on the hotplate surface and
briefly bring the flask to boiling. Cool the mixture to room temperature and then place it
in an ice bath for about 15 minutes or until crystallization appears to be complete. Filter
the product using a Bchner funnel, washing remnants out of the flask with deionized
water (2 x 5 mL). Wash with several small (2-3 mL) volumes of cold ethanol (make sure
you chill it first or it will dissolve your compound!). Allow the compound to dry until the
next lab period and then weigh the compound to get the yield of dry product.
B. Preparation of Cr(acac)3.2
Heat a water bath on a stirring hotplate. Add approximately 1.30 g of CrCl36H2O into a
50-mL Erlenmeyer flask. Drop in a small magnetic stirring bar, add 20.0 mL of distilled
water and stir briefly. When the chromium compound has dissolved into solution, add
5.0 g of urea and 4.0 mL of acetylacetone. Clamp the flask in place in the water bath
(see note in part A) and heat the water bath to a temperature greater than 90C. Heat
the mixture, uncovered and with vigorous stirring, for approximately one hour. As the
urea releases ammonia and the solution becomes basic, deep maroon crystals will
begin to form. After one hour, allow the reaction to cool to room temperature, and then
place it in an ice-bath to complete crystallization (Note: if you do not see solid after 1 h,
continue to heat and stir until you dosometimes it takes a bit longer!). Collect the
product by vacuum filtration using a Bchner funnel. Wash out the flask and the
crystals on the filter with plenty of deionized water (about 3 x 10 mL). Allow the product
to dry until the next lab period and then weigh the dry final product to determine the
yield of dry product.
C. Preparation of Mn(acac)3.3
Add approximately 1.0 g of MnCl24H2O and 2.6 g of sodium acetate trihydrate into a
100-mL Erlenmeyer flask. Add a stirring bar, and dissolve the solids in a minimal
amount of distilled water (add very small amounts at a time until the solids dissolve
completely). When the solids are dissolved, add 4.0 mL of acetylacetone with
continued stirring. Prepare another solution containing 200 mg of KMnO4 in 10 mL of
deionized water. Make sure you stir this for quite a whileKMnO4 is difficult to dissolve
and it color makes it hard to see if it has dissolved! Add the KMnO4 solution slowly and
drop-wise, with stirring, to the above mixture. After addition is complete, a small portion
of distilled water (1-2 mL) should be pipetted (using a disposable pipet) into the flask or

beaker originally containing the KMnO4 solution and then used to rinse the walls of the
reaction flask to remove any permanganate that is sticking to the side. After stirring the
mixture for about five minutes, add drop-wise a second 2.6 g portion of sodium acetate
trihydrate dissolved in a minimal amount of water. Heat the resulting mixture directly on
a hotplate for 10 minutes at about 70C (put a thermometer directly in the reaction flask)
and then set aside to cool to room temperature. Collect the dark brown precipitate on a
Bchner funnel. Use small portions of deionized water (2 x 5 mL) to wash any remaining
crystals out of the flask. Allow the product to dry until the next lab period and then
weigh the dry final product to determine the yield of dry product.
Part D. Preparation of Fe(acac)3.4
Add approximately 1.3 g of Fe(NO3)39H2O into a 50-mL Erlenmeyer flask and dissolve
in 7 mL of distilled water. Drop in a magnetic stir bar, stir the solution, and add a
mixture of 1.0 mL of acetylacetone in 7 mL of methanol. Next, add a solution
containing 1.3 g of sodium acetate trihydrate in 7 mL of distilled water, and briefly heat
the mixture on a hotplate until some of the methanol has boiled away (you should see
the volume of the reaction mixture go down). Cool to room temperature, and then place
in an ice bath for about 15 minutes. Filter the red crystalline solid using a Bchner
funnel, wash the flask and crystals, using 2 x 5 mL) of deionized water. Allow the
product to dry until the next lab period and then weigh the dry final product to determine
the yield of dry product.

II. Recrystallization
Crystallization of an inorganic (or organic!) product is often a critical step in a synthesis
procedure. It frequently allows you to purify the product, or to grow larger crystals that
are suitable for X-ray structural analysis. Since X-ray crystallographic analysis is
frequently necessary to identify definitively inorganic substances, this is an important
skill in inorganic chemistry. Unfortunately, in synthetic procedures, you will sometimes
be given little detailed information about how to carry out such a procedure, so you
need to learn to fly by the seat of your pants, so to speak, when it comes to purifying
your product through recrystallization. Although it can take multiple trials to get it right,
the procedures themselves are typically not very difficult.
You should use at least half of each compound for your crystallization attempts
sometimes it takes multiple tries to get something that works! You should at least try
one form of layering, and you can use either or both of the other methods as well. The
more things you try, the better luck you will have a growing large crystals. You should
definitely try more than one type of solvent combination. Each group member must
complete one recrystallization.
Note: Make sure that you have recorded the yield of your dry product before
starting this part of the lab!

Solubility Testing. The first step in any crystallization procedure is to determine the
solvents in which a product is soluble and insoluble. Typically solvents with a range of
polarities are tried, such as water, methanol, acetone, acetonitrile, methylene chloride,
ethyl ether, toluene, and pentane. Solubility tests can be done by placing a small
amount (the very tip of a spatula, just enough so you can just see it) of product in about
a 1/2 mL of solvent. Indicate the solubility of the compound as soluble, slightly soluble,
or insoluble. When you are testing solubilities, be on the lookout for significant color
changes to the productthis may mean that the product is decomposing in the solvent,
or that the solvent is coordinating (binding) to the product. Be sure to note this. Test
your compound for solubility in the range of solvents provided. Now continue, using one
or more of the methods described below to grow your crystals.
Layering. One of the best methods for crystallization is layering. This consists of
creating two layers of solvents, one more dense than the other. The layers are carefully
made so that there is as little mechanical mixing as possible; they will mix, however,
over time due to diffusion. After you have a list of solvents in which the compound is
soluble and insoluble, look them up on the solvent miscibility table. Try to find a solvent
in which the compound is soluble that is miscible with another solvent in which the
product is insoluble. Two solvents are immiscible if they form two unmixable layers, like
oil and water, and miscible if they can be mixed. If you add
enough of the solvent that the product is insoluble in to a solution
of the product dissolved in a soluble solvent, product will
precipitate from the solution. The more carefully the solvents are
added together, the better the chance for large crystals!
After identifying your choices of solvent, dissolve your compound
in the solvent in which it is soluble. Try to use a minimal amount of
Sample
solvent (your solution should be very darkly colored!). If the
compound does not dissolve completely in your initial solvent, you
can remove small particles by making a filter from a disposable
pipette and a small wad of a Kimwipe (see figure to the right).
Push the wad of paper down into the narrow part of the pipette.
The Kimwipe will serve as your filter. Then run your solution
through the top of the pipette to filter it! After you have a solution
of your product you will have to add this to the solvent in which the
Kimwipe
compound is insoluble. You can either add the insoluble solvent
very carefully on top of your solution of product, slowly dribbling it
down the sides of the vial using a pipette; this is the top-down
Crystallization
method. Alternatively, you can add the solution of product
vialof NMR tube
Top
underneath the insoluble solvent, by taking the pipette directly to
the bottom of the vial and then dispensing the solution; this is the
bottom up method. If you use this method, stop before you have
dispensed all of the liquid so you dont introduce a big bubble that will disturb the layers.

Either way, you should do this recrystallization in a container that can be closed up very
tightly, such as a small vial with a screw-cap lid or an Erlenmeyer flask with a stopper.
Do not use Parafilm to seal your flask as it is soluble in some of the solvents. If you are
careful, you should be able to layer one solvent on top of the other so that you have two
distinct layers. When these layers diffuse together slowly, crystals will (hopefully!) form
at the interface! Carefully put your solution somewhere it will not be bumped (such as in
the bottom cabinet of your lab drawer) and check on them periodically to see if crystals
are growing. If you dont see crystals, make sure your solution hasnt evaporated
through a leaky lid, that the initial solution of your compound is concentrated enough,
and that youve added enough of the insoluble solvent (adding more of the latter is a
quick thing to try if you dont get crystals the first time). Note: when designing your
layering, try to get the more dense solvent (you can look up densities in the Aldrich
catalog or by searching on Google) to be the one that ends up on the bottom, otherwise
the layers will mix immediately upon adding the second one!
Vapor diffusion. Vapor diffusion is similar to layering in that you use two solvents that
are miscible, one in which the compound is soluble and one in which the compound is
insoluble. Make a solution of the compound in the soluble solvent. Filter with a pipette
as described earlier to remove any small pieces of undissolved solid and place the
solution in a small open vial. Place the whole vial inside a bigger vial or a screw-cap
container of some sort (the stockroom has a variety you can check out) that contains a
bit of the insoluble solvent. Being careful not to tip the open vial, place a tight lid on the
bigger vial. As long as the solvents are reasonably volatile, they will change places
over time and increase the concentration of the insoluble solvent in the smaller vial until
crystals form and precipitate out of solution.
Slow Evaporation. Slow evaporation is perhaps the easiest method of crystallization,
however the timing is very important to make sure that you do not allow all the solvent
evaporate. Make a concentrated solution of your compound in the soluble solvent and
filter (as explained above) to remove any undissolved particles. Place that solution in a
small glass vial. Then either loosely cap the vial. Keep checking to ensure that the
solvent does not completely evaporate.

III. Infrared Spectroscopy

In order for acetylacetone to bind strongly to a metal ion, you first reacted it with base,
as shown here. Notice how many of the
H3 C
H3 C
bonds in the acetylacetone change as a
C
OH
C
O
result of this deprotonation. We might
expect to see evidence for these changes
+ base
HC
+ Hbase
HC
in the ligands infrared spectrum. We
C
O
might also expect to see a change in the
C
O
spectrum due to the ligands bond to the
H3 C
H 3C
metal. More specifically, we will be
looking at the C=O stretches in the acid form of the ligand with the proton still attached
and in the spectrum in the complex to learn about how that bond has changed.
6

Obtain an IR spectrum for each of the four compounds (see Lab 4 if you forget how)
and an IR spectrum of Hacac, the protonated form of the ligand.

Part IV. Visible Spectroscopy

As you have probably gathered through your experience in this class, transition metal
complexes, such as the ones that you just synthesized, exhibit a wide variety of colors.
The source of this color comes from the ability of valence electrons to absorb light and
move from more stable orbitals to less stable orbitals. When a photon from the visible
region of the electromagnetic spectrum (400 nm to 700 nm) is absorbed by a sample,
the remaining visible light reflects off (or passes through) the sample. Since white light
contains all wavelengths of visible light, what we see is the complimentary color of the
photons that were absorbed. For example, if blue wavelengths have been absorbed,
the remaining wavelengths produce an orange color; this is what we see. In a visible
spectrum we look at absorption as a function of wavelength. Peaks in the spectrum
show those wavelengths of light that are absorbed by the compound and provide
information about the electronic energy levels of the compounds valence electrons and,
consequently, information about the bonding in the compound.
While we will discuss in class the theory behind why some transition metal complexes
have different colors, a simple model is shown below. In an octahedral complex, the
d-orbitals are actually split into two energy
dx2-y2
dz2
levels: a triply degenerate (three orbitals at
10Dq
E
the same energy) and a doubly
or
degenerate level. An electrons transition

dyz
dxy
dxz
between these two sets of orbitals has an
energy, , and the energy of this gap
corresponds to photons in the visible region of the electromagnetic spectrum (because
this is a relatively small energy gap). The size of this energy gap and, therefore, the
wavelength of maximum absorption for a metal-ligand complex depends upon the
bonding in that complex. In general, the larger the energy gap between the orbitals, the
stronger the bonding between the metal and the ligands.
In order to take a visible spectrum, a sample of compound needs to be dissolved in a
solvent of some sort. The absorbance of a compound is proportional to the amount of
that compound that has been dissolved in solution. You should aim for a maximum
absorbance value of about 1.0 (absorbance values do not have any units associated
with them). Pick a solvent in which all of your compounds are soluble. Dissolve a
small amount of each compound in separate portions of the solvent (4-5 mL for each
should be sufficient). If there is any undissolved solid, filter the solution through a
disposable pipette fitted with a Kimwipe plug (as explained earlier) to obtain a clear
solution. The solution should have a pale color but discernable color. Obtain spectra for
each compound from 390 nm to 900 nm using the Ocean Optics Spectrometer.

Compounds and Waste Disposal

Instructions for your compounds are provided below in the section on reporting results.
All other waste, including the solutions used to obtain your visible spectrums should be
disposed of properly in the appropriate waste container.

Write Up
From each person I need the following:
I will need to inspect each persons recrystallization attempt in lab! During the last week
of lab, when we will be checking out of lab, show me the results of your crystallization
efforts.
From every group I need the following:
Your compoundsplace each compound in a vial and include the compounds name,
formula, mass of product and the name of the individual who synthesized the
compound.
For each compoundcopies of the IR and visible spectra of your four compounds.
In addition, answer the following questions in a neatly prepared report. Your answers
should be in the form of well-written, complete sentences. Good organization, proper
grammar and spelling matter.
1. Examine your IR spectra in the region between 1500 and 1700 cm-1. The bands in
this region are due to the ligands C=C and C=O stretches. The C=C stretch is the
one at higher energy. The C=O band is where you would most expect to see
changes as a result of the deprotonation and the binding of the ligand to the metal.
In general, in which direction (higher or lower energy) do the bands in this region
move upon binding to the metals? Which metal seems to have greatest effect on
the positions of these bands or are all of them approximately the same? Why do
you think this is so? Based on your knowledge of resonance structures, and the
bonding in Hacac and the M-acac complexes, explain the differences in the values
for the C=O stretching frequency. How would you expect the coordinate covalent
bonding of the oxygen to the metal to affect the amount of electron density in the
C=O bond and its bond strength? Is your prediction supported by the spectroscopic
evidence? If you generally see the same number of bands and the same shapes for
these bands, then the complexes likely have the same structure. Given your IR
spectra, do any of the complexes seem to have a different structure?
2. Examine your visible spectra and rank the four compounds from the strongest metalligand bond to the weakest metal-ligand bond. Clearly sight your evidence and your
reasoning.

3. Each of the reactions in Section I of the lab has an acid-base reaction and a
complexation reaction. For each compound write separate balanced chemical
reactions showing the acid-base reaction and the complexation reaction. Think
carefully about what species is acting as the base!
4. Several of the syntheses also involved a redox as well. Identify those compounds
that made use of a redox reaction and identify the oxidizing and reducing agents.

References
1. Bryant, B. E.; Fernelius, W. C. Inorg. Synth. 1957, 5, 188.
2. Charles, R. G.; Pawlikowski, M. A. J. Phys. Chem. 1958, 62, 440.
3. Fernelius, W. C., Blanch, J. E. Inorg. Synth. 1957, 5, 130.
4. Charles, R. G. Inorg. Synth. 1963, 7, 183.