Experiment 2: Synthesis and IR characterization of tris(acetylacetonato)iron(III)

Introduction

Coordination compounds (or complexes) consist of a central atom surrounded by various other atoms,
ions or small molecules (called ligands). There is only a tenuous distinction at best between coordination
complexes and molecular compounds. The most common dividing line is that complexes have more ligands than
the central atom oxidation number. Silicon tetrafluoride, SiF4, would not be a coordination compound, since there
are four ligands attached to the Si(IV). However, SiF62-, would be considered a coordination compound as there
are six ligands on the Si(IV). In this experiment, the coordination compound tris(acetylacetonato)iron(III) will be
synthesized and the resulting product will be characterized using infrared and nuclear magnetic resonance
spectroscopic techniques.

In the presence of base, 2,4-pentanedione (or acetylacetone - abbreviated acacH) loses a proton to form
the acetylacetonate anion (acac-), as shown:

Hydrogen atoms on α-carbon atoms that are adjacent to carbonyl groups, C=O, are relatively acidic. The three
different representations of the acetylacetonate anion are called resonance forms (they differ only in the location
of the electrons).

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Acetylacetonate is an example of a bidentate (bi-two, dent-teeth) ligand since it can bond to a metal via both
oxygen atoms, hence forming a six-membered ring (shown below). Ligands of this type are also often called
chelating (chelos-claw) ligands. Three acac- ligands are therefore needed to complete the octahedral coordination
about the central metal ion.

In pure acetylacetone, or in non-polar organic solvents, the diketo form is in equilibrium with a cyclic
enol-like structure:

The second tautomer may be regarded as a complex in which the proton H+ takes the role of the metal ion Mn+.

In general, the complexes isolated as crystalline solids are neutral so that a metal ion M n+ forms a
complex having the stoichiometry M(acac)n:

n acacH + M n+ → M(acac)n + n H +

In these complexes the M(acac) six-membered rings are planar and contain 6-π electrons. They may, therefore, be
regarded as weakly aromatic. The M(acac)3 complexes are octahedral and the C−C−C backbone of the ligand
bridges adjacent coordination sites around the central metal ion.

Nuclear Magnetic Resonance spectra of acetylacetonates

In this section, the 1H and 13

C NMR spectra of a diamagnetic metal acetylacetonate, Al(acac)3, and
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acetylacetone are examined and assigned. For the C spectra, shown on the following pages, several different
versions of the spectra were obtained using different pulse sequences. The C-H coupling in these 13C spectra is
suppressed ("proton-decoupled") so they are not displayed. The formal notation for a proton-decoupled carbon
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NMR spectrum is C{1H}. In the normal spectrum, all types of carbon environment (CH3, CH2, CH and
quaternary C) are displayed. In the DEPT spectrum, the resonances due to quaternary C are suppressed and those
due to CH2 are inverted, while in the DEPT-90 spectrum, only the resonances due to CH appear. Hence all four
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types of carbon environment can be readily identified. Table 2-1 contains a list of characteristic C chemical
shifts.
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 Table 2-1. Characteristic 13C Chemical Shifts
Type of carbon Representation Chemical shift range (δ ppm)
Primary alkyl 0 – 40

Secondary alkyl 10 – 50

Tertiary alkyl 15 – 50

Quaternary alkyl 35 – 45

Allylic 20 – 40

Alkyl halide or amine 10 – 65

Alkyl ether or alcohol 50 – 90

Alkyne 60 – 90

Alkene 100 – 170

Aryl 100 – 170

Nitrile 120 – 130

Amide 150 – 180

Carboxylic acid 160 – 185

Aldehyde or ketone 180 – 215

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Pre-lab Questions (to be submitted as .pdf online by 9:00 am on lab day):
1. Examine the 13C{1H} spectra of Al(acac)3 (Figure 2-1) and assign the resonances. Keep in mind that the
three ligands are all symmetrically equivalent (D3 molecular symmetry). Report the results in tabular
form.

2. Examine the 1H spectrum of Al(acac)3 (Figure 2-2) and assign the resonances. Examine both the peak
shifts and integrations. Report the results in tabular form.

3. Examine the 13C{1H} spectrum of acetylacetone (Figure 2-3). First, assign the resonances due to the enol
tautomer. Then, assign the resonances due to the diketo tautomer. Report the results in tabular form.

4. Examine the 1H spectrum of acetylacetone (Figure 2-4). First, assign the resonances due to the enol
tautomer. Then, assign the resonances due to the diketo tautomer. Examine both the peak shifts and
integrations. Report the results in tabular form.

5. Calculate the diketo:enol ratio of acetylacetone from the 1H NMR spectrum.

Hint: In acetylacetone, both diketo and enol forms are present. Since the enol form can be regarded as a
complex of H+, its 1H and 13C{1H} NMR spectra may be expected to show similarities with those of the
aluminum complex.

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Figure 2-1. 13C{1H} NMR spectrum of Al(acac)3 in CDCl3

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Figure 2-2. 1H NMR spectrum of Al(acac)3 in CDCl3

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Figure 2-3. 13C{1H} NMR spectrum acacH in CDCl3

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Figure 2-4. 1H NMR spectrum acacH in CDCl3

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Safety Notes:

Iron Trichloride Hexahydrate (CAS No. 10025-77-1): MW: 270.33 g mol-1. mp: 37 °C. Density: 1.82 g cm-3.
Yellow to brown crystals. Highly soluble in polar solvents e.g. water, alcohol, acetone, ether. Hygroscopic:
absorbs moisture or water from the air. Causes burns by all exposure routes. Harmful if swallowed. May cause
liver and kidney damage. May cause central nervous system effects. May cause cardiac disturbances. ORL-RAT
LD50: 200 mg/kg. NFPA Rating: Health: 3; Flammability: 0; Instability: 1

Sodium Acetate Trihydrate (CAS No. 6131-90-4): MW: 136.08 g mol-1. mp: 58 °C. Density: 1.42 g cm-3.
Deliquescent salt when anhydrous, used as food additive (salt and vinegar flavor on chips). The compound is a
mild irritant to mucous membranes. ORL-RAT LD50: 2,700 mg/kg. NFPA Rating: Health: 1; Flammability: 1;
Instability: 0

2,4-Pentanedione (CAS No. 123-54-6): MW: 100.12 g mol-1. mp: -23 °C. bp: 140.4 °C. Density: 0.975 g cm-3.
Also known as acetylacetone. The compound is a mild irritant to the skin and mucous membranes. It is a
flammable liquid. ORL-RAT LD50: 590 mg/kg. NFPA Rating: Health: 2; Flammability: 2; Instability: 0

Ethanol (CAS No. 64-17-5): MW: 46.07 g mol-1. mp: -114 °C. bp: 78 °C. Density: 0.789 g cm-3. Ethanol may be
fatal if inhaled, swallowed or absorbed through the skin in large amounts. It has been shown to have effects on
fertility and on embryo development. ORL-HMN LDLo: 1400 mg/kg. ORL-RAT LD50: 7060 mg/kg. NFPA
Rating: Health: 2; Flammability: 3; Instability: 0

Chloroform (CAS No. 67-66-3): MW: 119.37 g mol-1. mp: -63.5 °C. bp: 61 °C. Density: 1.489 g cm-3.
Chloroform is a potent narcotic agent. It may be fatal if inhaled, swallowed or absorbed through the skin. It is
classified as a carcinogen. Inhalation of large doses may cause hypotension, respiratory and myocardial
depression and death. IHL-HMN LCLo: 25,000 ppm/5M. ORL-RAT LD50: 908 mg/kg. NFPA Rating: Health:
2; Flammability: 0; Instability: 0

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Preparation of tris(acetylacetonato)iron(III), Fe(acac)3

𝐎𝐯𝐞𝐫𝐚𝐥𝐥: 𝐹𝑒𝐶𝑙3 + 3 acacH + 3 NaCO2 CH3 → Fe(acac)3 + 3 HCO2 CH3 + 3 𝑁𝑎𝐶𝑙 (1)

In this preparation, iron(III) chloride hexahydrate (FeCl3·6H2O) is used as our starting reagent,
which will react with the 2,4-pentanedione (a.k.a. acetylacetone) in the presence of sodium acetate (as
its trihydrate salt) according to equation (1) to form the desired Fe(acac)3 complex that we isolate. Note
that equation (1) ignores the hydrated water within our starting reagents (we are carrying out the reaction
in water anyways).

Carefully weigh into a 250 mL Erlenmeyer flask FeCl3·6H2O (1.4 g) and in your fume hood, add
~3 mL of distilled water and dissolve using a magnetic stir bar. In a separate beaker, weigh out ~2.5 g of
CH3CO2Na·3H2O and dissolve in ~5 mL of distilled water by gently swirling. Slowly add the
CH3CO2Na·3H2O solution using a pipette into the FeCl3·6H2O with constant stirring, and continue to
stir while you prepare the acetylacetone ligand solution. INSIDE YOUR FUMEHOOD, use a pipette
measure out the 2,4-pentanedione (2.0 g, use the density to determine what volume of liquid is required)
and dissolve it into ~5.0 mL of ethanol. Slowly add the 2,4-pentanedione solution to your iron solution
with constant stirring, and continue to stir for 5 minutes afterward to ensure the reaction is complete.
Collect the product by vacuum filtration using a Buchner funnel with filter paper, and wash the product
with a small amount of distilled water. Collect your crude product into a clean Erlenmeyer flask for
recrystallization.

To recrystallize your product, slowly add just enough ethanol to the Erlenmeyer until your
product just completely dissolves (approx. 15 mL max). Once dissolved, add distilled water (25 mL) to
the ethanol solution and gently swirl/stir. Crystals of your product should crash out of solution. Once
again, collect the crystalline product by vacuum filtering using a Buchner funnel with filter paper and
wash the product with a small amount (~ 2 mL) of cold ethanol (use ice bath to cool) three times. Very
gently loosen the crystalline solid on the filter paper and leave the vacuum filtration system going for
~15 minutes to aid the drying. Using a solid funnel, transfer your product to a scintillation and
remember to properly label your vial.

Weigh the crystalline red product and record the percentage yield. Determine and record the
melting point. You and your lab partner will collaborate for the IR analysis; one of will run an infrared
spectrum as a CHCl3 film (be sure that the chloroform has nearly evaporated from the surface of the
NaCl plate before running the infrared spectrum!) and the other will run their sample as an solid ATR-

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IR. You may work together with your fumehood (or assigned) partner only on the IR analysis and
comparison (see details below on informal lab report)

To be included in your Informal Lab Report

(template not required – due 6:00 pm on lab day as scheduled):
• Title, PRA section, your name, fumehood partner/collaborator name, TA name
• Briefly discuss the synthesis/reactions and any observations, percent yield with sample
calculation and melting point (compare to literature and explain any differences).
• In Collaboration with your fumehood partner only (you may submit identical work):
Examine and compare the infrared spectra of Fe(acac)3 obtained by both IR methods. You
should use the excel data to graph both spectra on the same graph (instructions provided).
Clearly identify and assign as many peaks as possible in tabular form – if there are some peaks
only in one or the other make sure to explain why. Among your assignments, in particular
discuss the C=O / C=C stretches. Make sure to compare your bands and assignments to those
observed in at least one other M(acac)x complexes in the literature to aid in your assignments.
What is the significance of any major differences? Hint: Use the references at the end.

Post-lab Questions (INDEPENDENTLY answered in separate section with Informal Report):

1. Examine the 1H NMR spectra of Fe(acac)3 (Figures 2-5). Rationalize why the spectrum looks so broad
and shifted compared to that of Al(acac)3 (Hint: consider and compare electrons and their configurations).
2. What is the purpose of sodium acetate in this synthesis and is there any experimental evidence that it
reacts to form a complex with iron?
3. What is atom economy within principles of green chemistry? Apply it to our preparation of Fe(acac)3
(ignore all hydrated/released water molecules in your calculations). What does this information tell you
about our synthesis, even if the reaction had a very high yield?
4. Our product, Fe(acac)3, can be used as a catalyst for many different organic reactions. Provide one
example reaction from the literature (make sure to give the reference).

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Figure 2-5. 1H NMR spectrum of Fe(acac)3 in CDCl3

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References:

(1) Seco, M. Acetylacetone: A versatile ligand. J. Chem. Educ. 1989, 66, 779.
(2) Bock, H.; Flatau, K.; Junge, H.; Kuhr, M.; Musso, H. Bond Character of β-Diketone Metal
Chelates. Angew. Chem. Int. Ed. 1971, 10, 225.
(3) Zielinski, T. J.; Grushow, A. Hydrogen Bonding Using NMR: A New Look at the 2,4-
Pentanedione Keto-Enol Tautomer Experiment. J. Chem. Educ. 2002, 79, 707.
(4) Lecomte, J. Infra-red adsorption spectra of metallic acetyl-acetonates. Discuss. Faraday Soc.
1950, 9, 125.
(5) Nakamoto, K.; McCarthy, P. J.; Ruby, A.; Martell, A. E. Infrared Spectra of Metal Chelate
Compounds. II. Infrared Spectra of Acetylacetonates of Trivalent Metals. J. Am. Chem. Soc.
1961, 83, 1066.
(6) Mikami, M.; Nakagawa, I.; Shimanouchi, T. Far infra-red spectra and metal—ligand force
constants of acetylacetonates of transition metals. Spectrochim. Acta A 1967, 23, 1037.
(7) Slabzhennikov, S. N.; Ryabchenko, O. B.; Kuarton, L. A. Distinctive and Regular Features of the
IR Spectra of Transition Metal Tris(acetylacetonates). Russ. J. Coord. Chem. 2008, 34, 551.

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