Inorganic Experimental Chemistry

First Semester 2020/2021

The course consists of two parts:

I. The theoretical part: 12-14 (one hour) lectures covering theoretical aspects of inorganic
synthesis.

II. The experimental part: The synthesis and characterization of complexes listed in 10 of
the following experiments:

1. [Cr(acac)3] and its derivatives [Cr(Br-acac)3] or [Cr(NO2-acac)3]

2. [Co(acac)3]
3. [Mn(acac)3]
4. [Co(NH3)6]Cl3, [CoCl(NH3)5]Cl2
5. Cis and trans K[Cr (ox)2(H2O)2] Cis and trans [CoCl2(en)2]Cl
6. [Ni(acac)2], [Ni(acac)2(H2O)2], [Ni(acac)2(py)2]
7. [Cr(acetate)2]2.2H2O
8. Cu-acac complexes.
9. K3[Fe(ox)3]. 3H2O

For each complex the following are carried out unless stated otherwise: melting point, percentage
yield calculation, molecular weight determination (for non-ionic compounds), conductivity
measurement (for soluble compounds), magnetic susceptibility, I.R. and U.V spectra. A report
involving full characterization of the prepared complexes must be submitted when the experiment
is finished.

The grades for the course will as follows

Lab reports 15 points
Quality of products 15 points
Evaluation of work 10 points
Midterm 20 points
Final exam 40 points
.
 Experiment 1

[Cr(acac)3] and its derivatives [Cr(Br-acac)3] or [Cr(NO2-acac)3]

General Introduction for acetylacetonato metal complexes.

Acetylacetone (Hacac) is one of the most famous ligands in coordination chemistry. The first
appearance of this ligand was in 1890s by Combes (Combes, 1890). At that time, Alfred Werner
published his work on this ligand and on similar ligands.(Werner, 1913). This ligand forms
complexes with different coordination numbers and with different structures with almost all
metals. Also these complexes are widely used as catalyst precursors and reagents. Cu(I)-acac is
employed to catalyze Michael additions. The Cu(II)-acac complex is used in catalyzed coupling
and in carbene transfer reactions.

The molecular formula of the ligand is C5H8O2 and its tautomeric keto and eno forms coexist in
solution(Scheme 1).

Scheme 1. Keto-eno forms of acetylacetone.

The mechanism of binding acac to metals can be described as following. The acidic proton on α-
carbon has a pKa = 9, once this proton is removed, it results in a negatively charged species with
delocalized negative charge along ß-diketone. At this stage, the acac can chelate easily to
metals. This acetylacetonato ion (acac-) can be represented by three resonance structures
(structures A to C), or can be represented by the resonance hybrid (D) as shown in scheme 2.

Scheme 2. The three resonance structures A, B and C and the resonance

hybrid (D) of acetylacetonato anion.

 Different metal acac complexes have been prepared. Examples are M(acac)3 where M=Cr(III),
Co(III), Fe(III) and Mn(III) with coordination number of 6 with almost octahedral coordination.
The Cu(acac)2 complex is a square planar structure. VO(acac)2 and Zn(acac)2H2O are
pentacoordinate complexes, having a square pyramidal structure. Anhydrous Ni(II) and Co(II)
acetylacetonato complexes are trimer and tetramer with the molecular formulas [Ni(acac)2]3 and
[Co(acac)2]4 respectively. The complexation mode between acac and Ir(III) and Pt(II) is
different, the ligand binds metals ions through the central carbon atom (C3) and these complexes
are classified as organometallic complexes.
Chromium(III) ion is the most stable oxidation state for chromium ion in aqueous solution, it
exists as hexaquachromium(III) ion. Chromium(III) forms stable complexes with various ligands
including oxygen and nitrogen donor ligands. Due to its high crystal field stabilization energy,
reactions of chromium(III) ion are slow and once Cr(OH)3 is formed it remains unreacted. Hence
special care must be taken in the synthesis of chromium(III) complexes in basic solutions. In this
experiment tris(acetylacetonato)chromium(III) is first prepared and from it either its bromo or its
nitro derivative is prepared.
To avoid excess base and hence the formation of the inert Cr(OH)3, acetylacetone is
deprotonated in situ by low concentration of ammonia produced from the hydrolysis of urea:

(NH2)C=O + H2O →2NH3 + CO2

-
Instead of strong base like NaOH, ammonia is hydrolyzed to produce OH in aqueous solution,
which removes the acidic hydrogen in acetylacetone in the presence of the chromium ion.

The bromo derivative of tris(acetylacetonato)chromium(III), Cr(Br-acac)3 is prepared by the

bromination of tris(acetylacetonato)chromium(III) using N-bromosuccinimide (NBS) (Collman,
1965), while its nitro derivative, Cr(NO2-acac)3 is prepared by the nitration of
tris(acetylacetonato)chromium(III) using copper nitrate/acetic anhydride mixture. (Collman, et
al., 1962; Collman, et al., 1963; Collman, 1965; Schirado, et al., 1971).

Prior Reading and Techniques

Inert and labile metal complex.

Visible spectra of Chromium(III) complexes.

Infrared spectra of acetylacetonato metal complexes.

Molecular weight determination using freezing point depression technique.

Crystallization using solvent mixture.

Pre lab Questions

1. Explain why octahedral Cr(III) complexes have high CFSE and hence are inert.
2. Write chemical equations to represent the bromination by NBS.
3. In acetone the alkyl hydrogen(hydrogen on α-carbon) is difficult to remove in the
presence of base, while in acetylacetone the proton is readily deprotonated in the
presence of base. Explain.
4. How can you estimate the octahedral splitting (Δo ) of octahedral Cr(III) complexes for their
visible spectra ?

Safety Recommendation.

2,4-Pentanedione: This compound is a mild irritant to the skin and mucous membrane

and it is flammable liquid. Avoid skin contact and keep in the fume hood.

Chromium(III) chloride hexahydrate: Mild toxic, avoid skin contact wash hands after use.

Tris(acetylacetonato)chromium(III): Harmful if swallowed or inhaled

N-bromosuccinimide: Harmful if swallowed, inhaled or absorbed through skin.

Copper(II) nitrate: Harmful if swallowed, inhaled or absorbed through skin.

Acetic anhydride: lachrymatory and may react violently with water if added too fast.

Benzene: This compound classified as a carcinogen. Avoid contact with the skin. Avoid
breathing the fumes. Use only in the fume hood.

Carbon tetrachloride: This compound is classified as a carcinogen. Avoid contact with the skin.
Avoid breathing the fumes. Use only in the fume hood.

Most organic solvents are flammable, keep away from direct flame..

Reagents Required
CrCl3.6H2O, 5.32 g.

Acetylacetone, 11.8 mL, 11.50g,

Urea, 20 g.

N-bromosuccinimide, 1.6 g,

Biphenyl, 20 g.

Copper(II) nitrate trihydrate,2.15 g,

5% aqueous NaHSO3 solution,10 mL.

Sodium acetate, 15 g.

Acetic anhydride, 40 mL.

Pet. Ether(100 mL), chloroform ( 50 mL), 95% ethanol (50 mL), benzene (100 mL).

Experimental Procedures:

a) Synthesis of Tris(acetylacetonato)chromium(III).

1. Place 100 mL of distilled water in a 250 mL Erlenmeyer flask and add to it 5.32 g of
chromium(III) chloride hexahydrate,CrCl3.6H2O. After the chromium salt has dissolved add 20
g of urea and 11.8 mL of acetylacetone. Cover with a watch glass and clamp the Erlenmeyer
flask in a large beaker containing water. Heat the water to boiling and keep it boiling mildly
for 2 hours. After a while a deep maroon crystal will begin to form as the urea releases
ammonia and solution becomes basic.

2. Remove the reaction flask from hot water (be careful, use towel) cool to room temperature by
placing the flask in a beaker containing cold water, and then collect the product by suction
filtration, wash the crystals with several small amounts of distilled water.

3. Transfer the crystalline product to a watch glass (or large filter paper) and allow it to dry in air.
(or you can dry in oven at temperature less than 100 oC.)

4. The product can be recrystallized from benzene / pet.ether as follows. (Be sure that the
complex is dry before this step and use dry Buchner funnel and dry suction flask) .

Dissolve 2.0 g of the product in minimum amount of warm benzene( use steam bath inside
the fume hood), add hot pet. drop wise with swirling or stirring until turbidity begins to appear.
Add few drops of hot benzene until turbidity disappears and leave to cool slowly. Cool in an
ice bath and collect the crystals by suction filtration, wash with pet. ether and dry in air.
5. Record the melting pint of the compound, its visible spectrum in chloroform, its I.R. spectrum
and its magnetic measurements. Measure the conductance of the compound in acetone.

6. Determine the molecular weight of the compound by measuring the freezing point depression
of its solution in biphenyl using an apparatus similar to that used in first year chemistry
laboratory, and as follows:
Obtain from the stockroom the molecular weight apparatus shown in figure1.1.

First determine the freezing point of biphenyl by placing about 1.70 g of biphenyl(weighed to
the nearest 0.001g )in the small test tube, it is better not to introduce the thermometer at this
stage. Heat using water bath to melt the biphenyl, introduce the thermometer and heat to about
80oC. Allow to cool slowly to about 60oC with mild stirring until temperature remains
constant while the compound solidifies, record this temperature. Repeat measurement again
using same sample in the tube.

To determine the freezing point of the solution, add to the above tube containing the biphenyl
about 0.35g Cr(acac)3 (weighed to the nearest 0.001g), reassemble the freezing point
apparatus, heat in water bath to produce a clear solution. Cool slowly in air and record the
 temperature when first traces of solvent crystals start appearing. Kf for biphenyl is
8.00oC/molal. Clean and dry the small inner test tube and return the apparatus to the stockroom
Calculate the molar mass of the complex, Cr(acac)3.

b) Synthesis of Tris(bromo-acetylacetonato)chromium(III).

1. Add 1.6 g (8.8 mmol) of NBS to a solution of 1.0 g of Cr(acac)3 in 15 mL chloroform. Boil in
the fume hood with shaking for 5 minutes. Use hot plate to boil the mixture. The solution should
turn green, and a brown precipitate should form. Transfer the mixture to an evaporating dish or
beaker, place in the fume hood to allow the solvent to evaporate to about 5 mL.

2. Collect the brown solid by suction filtration. Wash successively with 5 mL of 95% ethanol,
two 5mL portions of 5 % aqueous NaHSO3, 5 mL of water and two 5mL portions of hot 95%
ethanol.

3. Air dry the product and recrystallize it from benzene/pet.ether. Determine the melting point of
the complex, and its molar mass as described above. Obtain the visible and IR spectra of the
complex and a its magnetic measurements.

4. Record the melting pint of the compound, its visible spectrum in chloroform, its I.R. spectrum
and its magnetic properties, measure the conductance of the of the compound in acetone and
determine its molecular weight using freezing point depression method (as in exp1).

c) Synthesis of Tris(nitro-acetylacetonato)chromium(III).

1. Stir 2.15 g (8 mmol) of finely ground copper(II) nitrate trihydrate in 40 mL of acetic anhydride
o
at 0 C for 15 min. Some of the copper compound will dissolve to a deep blue solution.

o
2. Add 1.0 g (2.8mmoles) of Cr(acac)3 and stir the slurry at 0 C for one hour and then at 15 g of
sodium acetate at room temperature for 45 minutes. Pour the reaction mixture slowly and
carefully into a mixture of 120 mL water, about 120 g of ice and 15 g of sodium acetate while
stirring.
Caution: acetic anhydride may react violently with water if added too fast.

3. Collect the resulting dark red precipitate by suction filtration. Wash with 5 ml water and then
with 5 mL ethanol and air dry.
 4. Record the melting pint of the compound, its visible spectrum in chloroform, its I.R.
spectrum and its magnetic properties, measure the conductance of the of the compound in
acetone and determine its molecular weight using freezing point depression method (as in
exp1).
Questions

1. Why the strong base, NaOH, was not used to make the solution basic instead of urea? What are
some of the possible products of you added strong base directly?
2. Compare the I.R spectra of acetylacetone with those of chromium acetylacetonato complexes,
especially in the region of C=O stretching frequency. Explain your results.
3. How many absorption maxima are observed in the visible spectra of chromium acetylacetonato
complexes? Are these d-d transitions? Explain assuming octahedral geometry around
chromium(III) ion.
4. Which band in the visible spectra of chromium acetylacetonato complexes represents ∆o for these
complexes? Compare values for the complexes you prepared and explain difference.

References

1. Fernelius,W.C.; Blanch,J.E. Inorg. Syn. 1957,5,130.

2.Charles,R.G. Inorg.Syn. 1963,7,183.

3. Fackler,J.P.,Jr,”Metal β-Ketoenolate Complexes” in Progress in Inorganic Chemistry,

F.A.Cotton, Ed., Interscience: New York, 1966,Vol.7.p.471.
4. Cotton,F.A.;Wilkinson,G. “Advanced Inorganic Chemistry”,4th Ed.1980. John Wiley & Sons
Inc.
 Experiment 2
[Co(acac)3]

The Co(III) complexes have six d electrons, and in this experiment you will determine whether
the compound is low-spin(diamagnetic) or high-spin (paramagnetic) spin (Remember, the
7 2 III 6
electronic configuration of Co is [Ar]3d 4s and of Co is 3d ).

Reagents Required:

Cobalt(II) carbonate, 2.5 g .

Acetylacetone, 20 mL
10% H2O2, 60 mL
Benzene, 50 mL
Pet. Ether, 300 mL

Purpose:
Preparation of tris (acetylacetonato)cobalt(III), by oxidation of Co(II)/acetylacetonate complex
produced from the reaction of acetylacetone and cobalt(II) carbonate. The complex is purified by
recrystallization from benzene/pet.ether and is characterized by m.p., conductivity measurement,
magnetic measurements and I.R. and visible spectroscopy.

Experimental Procedure:

This complex is prepared by the method of Bryant and Fernelius [Bryant, BE and Fernelius WC
Inorg. Syn. 188 (1957)].

1. A mixture of 2.50 g of powdered cobalt(II) carbonate and 20 mL of acetylacetone in a 250 mL

o
Erlenmeyer flask is heated to 90-100 C on a hot plate/stirrer. While stirring vigorously using
the magnetic stirrer, carefully add 30 mL of 10% (or 20%) hydrogen peroxide drop wise
(about 15 minutes, at a rate of 1-2 mL/min). Care must be taken during the initial minutes of
the reaction not to add the H2O2 too rapidly, since considerable heat is evolved and rapid gas
evolution causes frothing. After addition is complete heat to boiling.
2. Cool the mixture in an ice bath for 15 minutes and filter the dark green solid, wash with water
and small amount(10 mL) of cold ethanol. The product is dried at 100 oC( use oven with
temperature not exceedong100 oC).

3. Recrystallize the product from benzene/hexane solution. Filter the crystals and wash with
 hexane and dry in air. Weigh the product and calculate the percentage yield.

4. Record the melting pint of the compound, its visible spectrum in chloroform, its I.R. spectrum
and its magnetic properties, measure the conductance of the of the compound in acetone and
determine its molecular weight using freezing point depression method (as in exp1).
Questions
1-Assume that the reaction you carried out proceed in two steps:

(a) reaction to produce Co(II)/acetylacetonate and

(b) oxidation of this complex by H2O2.

Write separate balanced equations for these steps.

2- If the red-purple solution of Co(acac)2 in certain solvent is allowed to stand for several weeks
exposed to air, it slowly turns green. What is reaction? What is the driving force?

3. How many absorption maxima are observed in the visible spectrum of Co(acac)3? Are these
d-d transitions? Explain assuming octahedral geometry around cobalt(III) ion. Based on its
visible spectrum, do you expect Co(acac)3 complex to be diamagnetic or paramagnetic?
Explain.
 Experiment 3
[Mn(acac)3]

III
The Mn complex has four d electrons, in this experiment you will determine whether the
5 2
compound is high or low spin (Remember, the electronic configuration of Mn is [Ar]3d 4s and
III 4
Mn is 3d )

Reagents Required

Manganese(II) sulfate tetrahydrate, MnSO4.4H2O, 2.23 g

Acetylacetone, 8.00 mL,

Sodium acetate trihydrate, 10.4 g.

Potassium permanganate, KMnO4, 0.40 g

Pet. Ether(100 mL), benzene (100 mL).

Purpose:
Preparation of tris( acetylacetonato)manganese(III) complex. The complex is purified by
recrystallization from benzene/pet.ether and is characterized by m.p., conductivity measurement,
magnetic measurement and I.R. and visible spectroscopy.

Experimental Procedure:

1. Place 2.23g manganese(II) sulfate tetrahydrate (MnSO4.4H2O)(10 mmol) and 5.20 g sodium
acetate trihydrate (NaCH3COO.3H2O)(38.2 mmol) in a 250 mL Erlenmeyer flask equipped with
magnetic stirring bar. Place the flask atop a magnetic stirrer-hot plate; add 80 mL water and stir
the mixture to dissolve all the solid, when dissolution is complete add 8.00 mL
acetylacetone(76.8 mol).
2. In a 100 mL beaker dissolve 0.40 g potassium permanganate (KMnO4)(2.54 mmol) in 20 mL
water, add this solution slowly drop wise (use dropper) with stirring to the above reaction
mixture. After stirring for 5 minutes, add a second portion of 5.20 g sodium acetate trihydrate
dissolved in 20 mL water (drop wise). (Be sure to add all KMnO4 solution, remove 2-4 mL of
 the reaction solution, add it to the beaker used for KMnO4 rinse it and return the solution to the
reaction flask).
3. Heat the mixture to near boiling on a magnetic stirrer hot plate for 10 minutes, allow the
mixture to cool to room temperature.
4. Collect the dark brown precipitate by suction filtration, wash it with 20 mL water and dry in
vacuum oven(or in an oven at 80 oC).
5. Recrystallize the product from benzene/hexane solution. Filter the crystals and wash with
hexane and dry in air. Weigh the product and calculate the percentage yield.
6. Record the melting pint of the compound, its visible spectrum in chloroform, its I.R. spectrum
and its magnetic properties, measure the electrical conductance of the compound in acetone and
determine its molecular weight by freezing point depression method(as in exp1).

Questions
1. Write balanced equations for all reactions involved. Why KMnO4 was added? Explain the
rough ratio of Mn(II)/Mn(VII) of 4:1.
2. Mn(II) is nearly colorless, while Mn(acac)3 is colored, explain. Why Mn(VII) is very dark
violet?
3. The structure of Mn(acac)3 is quite different from those of Cr(acac)3 and Co(acac)3, explain.
4. Explain the visible spectrum of Mn(acac)3 complex. Does the complex show Jahn-Teller
distortion? Explain
 Experiment 4
Hexaminecobalt(III) chloride [Co(NH3)6]Cl3 and Pentaminechlorocobalt(III) chloride
[CoCl(NH3)5)]Cl2

A) Synthesis of Hexaminecobalt(III) chloride,[Co(NH3)6]Cl3

Reagents Required

Ammonium chloride, NH4Cl, 3.0 g.

Cobalt(II) chloride hexahydrate, CoCl2.6H2O, 4.5 g.

Activated charcoal, 0.10 g.

Con. Ammonia solution, 16 mL.

30% H2O2, 9.0 mL.

Con.HCl, 6.2 mL.

Acetone, 20 mL.

Experimental Procedure:

1. Dissolve 3.0 g of ammonium chloride and 4.5 g of cobalt(II) chloride hexahydrate, CoCl2.6H2O
in 7 mL boiling water. Add 0.10 g activated charcoal and cool in ice. Add 10 mL of
concentration ammonia solution and keep the mixture at 10oC or lower. Add slowly, in small
portions, 9 mL of 30% H2O2, briskly shaking the solution during the addition. Raise the
temperature to 10oC and then gradually to 50-60 oC, and keep the flask at this temperature,
with frequent shaking, until the last trace of pink coloration is removed (one hour).
2. Cool and collect the precipitate by suction filtration. Transfer the solid to a beaker containing a
boiling solution of 1.2 mL conc. HCl in 40 mL water. When all solid, except charcoal, has
dissolved, filter the solution while hot, add 4 mL of conc. HCl to the filtrate and cool the
solution in ice. (You may test solution with litmus to be sure it is acidic, add more HCl if
necessary).
3. Filter the golden-brown crystals on Buchner funnel, wash with acetone and allow to dry in air.
Weigh the product and calculate the % yield.

4. Record the melting pint of the compound, its visible spectrum in water, its I.R. spectrum
and its magnetic properties. Measure the conductance of the of the compound
in 10-3 M aqueous solution
B) Synthesis of Pentaminechlorocobalt(III) chloride, [CoCl(NH3)5)]Cl2

Reagents Required

Ammonium chloride, NH4Cl, 5.0 g.

Con. Ammonia solution, 40 mL.

Cobalt(II) chloride hexahydrate, CoCl2.6H2O, 10 g.

30% H2O2, 9 mL.

Con.HCl, 140 mL.

95% ethanol

Acetone, 20 mL.

Experimental Procedure:

1. In a fume hood, add 5 g of ammonium chloride to 30 mL concentrated aqueous ammonia in

a 250-mL Erlenmeyer flask. (The combination of NH4Cl and NH3(aq) guarantees a large
excess of the NH3 ligand.) Stir the ammonium chloride solution vigorously using a magnetic
stirring plate while adding 10 g finely divided (powdered) CoCl2.6H2O in small portions. A
yellow-pink precipitate of hexamine cobalt(II) chloride forms with the evolution of heat.

2. Next, add 9mL 30% hydrogen peroxide to the brown slurry, using a buret that has been set
up in the hood and filled by the laboratory instructor. An addition rate of about 2 drops per
second is usually sufficient, but care should be taken to avoid excessive effervescence in
this exothermic reaction. (If the reaction shows signs of excessive effervescence, turning off
the magnetic stirrer momentarily will usually prevent overflow of the solution.) When the
effervescence has ceased, add 30 mL conc. HCl with continuous stirring to the resulted deep
red pentamineaquacobalt(III) complex, pouring about 1-2 mL at a time. During
neutralization, the temperature of the reaction mixture rises, and the purple product
precipitates, leaving a pale blue-green supernatant liquid. At this point, the reaction may be
removed out of the hood.

3. Use a heater to heat the solution to 60°C with occasional stirring. Hold the temperature
between 55°C and 65°C for 15 min., this incubation period is necessary to allow complete
displacement of all aqua ligands.

4. Allow the solution to cool to room temperature. Collect the purple product by filtration using
a Büchner funnel; wash it three times with 7.5 mL cold distilled water three times with 7.5
mL cold 6 M HCl. Wash the product with ethanol and with acetone and dry in the oven at
 100-110 oC for 1 to 2 hours. Weigh the product and calculate the % yield.

5. The product is pure enough for most further synthetic work, but may be recrystallized as
follows with about 95% recovery: The solid is dissolved in 90 mL of aqueous ammonia (1M)
by warming gently on the steam bath, after which the clear solution is poured (work in fume
hood) into 90 mL of concentration HCl. After heating for 45 minutes on a steam bath, the
complex salt is isolated as above.
6. Record the melting pint of the compound, its visible spectrum in water, its I.R. spectrum and
its magnetic properties. Measure the conductance of the compound in10-3 M aqueous
solution.

Questions

1. Suggest magnetic moment for each of the two cobalt amine complexes prepared. Compare
the theoretical values with the experimentally obtained values.

2. Sketch the structure for the two cobalt amine complexes. How does the conductivity
measurement help you in deciding whether chloride ions are bonded to cobalt ion or not.
 Experiment 5

Cis and trans K[Cr (ox)2(H2O)2]

The diaquabis(oxalato)chromate(III) anion forms many well crystallized salts with various cations.
Their constitution was first established by Rosenheim and Cohn' and by Werner and Surber. The
salts occur in two geometrically isomeric series cis, reddish violet, and trans pinkish red-which are
formed by reduction of dichromates ion by oxalic acid; the specific conditions of the reaction
determine which isomer is formed. In aqueous solution the equilibrium between the cis-and trans-
[diaquabis(oxalato)chromate(III)] ions lies almost completely on the side of the cis isomer; pure
crystals of the slightly soluble potassium salts of the trans isomer are formed by the slow
evaporation of the solution at room temperature, whereas the potassium salt of the cis isomer is
obtained by cooling the hot solution or by allowing potassium dichromate and oxalic acid to react
with only a minimal amount of water present , this method is used given in this work.

A- Synthesis of potassium cis-[diaquabis(oxalato)chromate(III)] dihydrate

K2Cr2O7 + 7H2C2O4.2H2O →2 cis-[KCr(C2O4)2 (H2O)2].2H2O + 6CO2 + 13H2O

Reagents Required
Potassium dichromate, K2Cr2O7, 4.00 g.
Oxalic acid dihydrate, 12 g.
95% ethanol, 50 mL.
Ether,10 mL.
Conc.HCl, 10 mL.

Experimental Procedure:

1. A mixture of 4.00 g (0.0136 mol) of potassium dichromate and 12.0 g (0.0952 mol) of oxalic
acid dihydrate is ground together as thoroughly as possible in a dry mortar. The mixture is placed
in a compact pile in the center of a 10-cm evaporating dish whose inner surface has been
moistened with water. The dish is covered with a watch glass and placed on a hot plate that is
just hot to the touch. A spontaneous reaction with vigorous effervescence begins almost
immediately, and the mixture liquefies to deep purple syrup.

2. When the reaction appears complete (~5 min), 20mL of 95% ethanol is added, warming is
continued, and the mixture is triturated, first with a spatula and then with a pestle, until the
mixture solidifies. If solidification does not occur, the ethanol is decanted, an additional 20
mL of ethanol is added, and the trituration with warming is continued until the product is
completely granular. The deep-purple product is collected on a Buchner funnel, washed with
two 5-mL portions of 95% ethanol, 5 mL of ether, and then air dried. Weigh the product and
calculate the percentage yield.
 3. Record the melting pint of the compound, its visible spectrum in water, its I.R. spectrum(in
KBr pellets) and its magnetic properties. Measure the conductance of the of the compound
in 10-3 M aqueous solution.
B) Synthesis of potassium trans -[diaquabis(oxalato)chromate(III)] dihydrate

K2Cr2O7 + 7H2C2O4.2H2O →2 trans-[KCr(C2O4)2 (H2O)2].2H2O + 6CO2 + 13H2O

Reagents Required
potassium dichromate, K2Cr2O7, 4.00 g.
Oxalic acid dihydrate, 12 g.
95% ethanol, 50 mL.
Ether,10 mL.
Dilute HCl, 10 mL.
Dilute ammonia solution.

1. A solution of 4.00 g (0.0136 mol) of potassium dichromate, dissolved in a minimum volume

(ca. 8 mL) of boiling water, is added with stirring in small portions (Caution. vigorous
effervescence occurs) to a solution of 12.0 g (0.0952 mol) of oxalic acid dihydrate, dissolved
in a minimum volume (~17 mL) of boiling water in a 400-mL beaker.

2. The beaker is covered with a watch glass while the reaction proceeds (ca. 5 min). The solution
is allowed to cool to room temperature; then the dark-purple solution is transferred to a 6-cm
evaporating dish and is allowed to evaporate at room temperature to ca. one-third of its
original volume.

3. The deposited crystals are collected on a Buchner funnel, washed with three 10-mL portions of
ice water and 10 mL of 95 % ethanol, and then air-dried. Weigh the product and calculate the
percentage yield. If the trans isomer is contaminated with cis isomer, dilute aqueous ammonia
solution is added in small amounts with stirring and green solution is decanted, the process is
continued until no further green solution is formed. The remaining solid is collected by suction
filtration, washed with a little ice-cold water, and reconverted to the salt of the trans isomer by
adding dilute hydrochloric acid. The pure salt of the trans isomer is washed with ice cold water
and ethanol, ether, and air dried as above. Weigh the product and calculate the % yield.

4. Record the melting pint of the compound, its visible spectrum in water, its I.R. spectrum(in
KBr pellets) and its magnetic properties. Measure the conductance of the of the compound
in 10-3 M aqueous solution.

Question

Examine the visible spectra of the two isomers, can you explain the difference in the two
spectra? Which complex is expected to have more bands? Which complex is expected to have
higher molar absorptivity? Explain.
 Experiment 6
[Ni(acac)2(H2O2], [Ni(acac)2(Py)2] and [Ni(acac)2]

Purpose
Preparation of bis(acetylacetonato)diaquanickel(II), anhydrous bis(acetylacetonato)nickel(II), and
bis(acetylacetonato)dipyridinenickel(II) complexes.

Reagent Required
Acetylacetone, 11 mL
Sodium hydroxide, 4.0 g
95% ethanol, 250 mL.
Nickel sulfate hexahydrate,13.0 g
Pyridine, 5.0 mL

Experimental Procedures:

A) Bis(acetylacetonato)diaquanickel(II)

1. Dissolve acetylacetone (11 g) in 1.0 M sodium hydroxide solution (4.0 g NaOH in 100 mL
water). Add further acetylacetone drop by drop until a drop remains undissolved, and then just
add enough ethanol to dissolve it. Add to this solution, with stirring, nickel sulfate hexahydrate
(13 g) in water (50 mL).

2. Filter the precipitate on Büchner funnel, dry it in air (not in the oven) and recrystallize it from
hot ethanol (~200 mL). The product crystallizes in light blue-green needles.

3. Dry the product in air or in an oven at temperature less than 80oC. Weigh the product and
calculate the percentage yield.

4. Record the melting pint of the compound, its visible spectrum in ethanol, its I.R. spectrum
and its magnetic properties, measure the conductance of the of the compound in ethanol and
determine its molecular weight by freezing point depression method(as in exp1).

B) Anhydrous bis(acetylacetonato)nickel(II)
Weigh precisely about 2 grams of the prepared bis(acetylacetonato)diaquanickel(II) in a
preweighed dry sample tube 100oC and under vacuum for one hour, allow to cool to room
temperature and weigh the sample tube containing the sample and calculate the mass loss.
The anhydrous nickel(II) complex is dark green. Record the melting pint of the compound, its
 I.R. spectrum and its magnetic properties.

C) Bis(acetylacetonato) bis(pyridine)nickel(II)

1. Heat 3.0 grams of bis(acetylacetonato)diaquanickel(II) with a mixture of pyridine (5mL) and

ethanol (10 mL). Upon cooling the solution, blue crystals of
bis(acetylacetonato)bis(pyridine)nickel(II) appear. Filter the crystals on Buchner funnel, wash
with small amount of ethanol and dry in air. Weigh the product and calculate the % yield.
2. Record the melting pint of the compound, its visible spectrum in ethanol, its I.R. spectrum
and its magnetic properties, measure the conductance of the of the compound
in ethanol and determine its molecular weight by freezing point depression method (as in exp1).

Questions
1. Explain the spectra of both the diaqua and the bispyridine complexes.
Explain any difference. Which of the two has higher ligand field splitting? Explain. Do you
observe any distortion? Explain the presence of extra bands in the spectra.
2. Suggest the structures of the three complexes. Can the I.R. spectra or the magnetic moments be
used for the assignment of the structures.
3. Which complex shows lower C-O stretching frequency, [Ni(acac)2(H2O2 or [Ni(acac)2]?
Explain.
 Experiment 7

Diaquachromium(II) acetate dimer

Zn(s) + 2HCl →ZnCl2 + H2(g)

3+ 2+
2Cr + H2 →2Cr + 2H+
2+ -
Cr + 4OAc + 2 H2O →[{Cr(OAc)2}2. 2H2O]

Purpose
2+ 3+
Preparation of chromium(II) acetate by the reaction of Cr (produced from the reduction of Cr
by Zn/HCl), and acetate ion. The compound is diamagnetic, which is the property used to
test it for impurities of the paramagnetic Cr(III) compounds.

Reagents Required

CrCl3.6H2O , 15 g.
Zinc powder, 12 g
Sodium acetate trihydrate, 45 g.
Concentrated HCl, 25 mL.
Ice-cold, pre-boiled water, 200 mL.
95% ethanol, 75 mL.
Ether, 75 mL.

Experimental Procedure:

1- Assemble the apparatus shown in Fig. 1.1. A 500 mL filter flask is fitted with a two-hole
rubber stopper through which passes a small dropping funnel (50- or 100-mL funnel) and a
glass tube that reaches to within 1mm of the bottom of the flask. The side tube of the flask is
connected with a short piece of rubber tubing to a tube that dips about 1cm beneath the surface
of water in a breaker.

2- Remove the stopper and place the zinc powder and a solution of chromium(III) chloride in 50
mL of water in the suction flask. Replace the stopper and the dropping funnel and tubing.
 Place the hydrochloric solution in the dropping funnel and add slowly to the chromium(III)
chloride solution until the solution has a clear blue color. The acid must not be added too
rapidly or the solution may froth over through the side tube.

3-Meanwhile, make slurry of sodium acetate in 80 mL of water and place it into the 250 mL
Erlenmeyer flask. While hydrogen is still being rapidly evolved, pinch the rubber tubing (to
close it) so as to force the chromium(II) chloride solution over into the sodium acetate solution
in Erlenmeyer flask. Dip the delivery tube under the sodium acetate solution during the transfer.
A red precipitate of chromium(II) acetate forms. Immediately stopper the flask and cool by
swirling in running water.
Note: Do not add the chromium solution to the acetate solution unless the chromium solution is
a pure blue, a muddy blue or greenish-blue color indicates the presence of chromium(III)
compounds, which will cause the formation of difficult to filter chromium(III) hydroxide.

Apparatus for the Preparation of aquachromium(II) Acetate Dimer

4- Filter the chromium(II) acetate complex on a Buchner funnel and wash it with four 50-mL
portions of cold air free water. Air free water can be obtained by boiling it for few minutes, or
by bubbling oxygen-free nitrogen gas through it for five minutes.

5- Do not stir up the precipitate with the wash water very much or the filtration may proceed slowly.
Wash the precipitate with alcohol and then with ether, and finally suck the crystal as dry as
possible on the funnel. Be careful not to suck air through the precipitate when it is wet with
water or alcohol. Spread the product thinly on watch glass and allow it to dry thoroughly at room
temperature. A better way to dry the product is to place it in a vacuum desiccator and reduce its
pressure using a vacuum pump; this will prevent any oxidation of the product.
Note: Sometimes when the chromium(II) is being dried on the funnel or on a watch glass, a
portion of the material turns from brick red to gray green color. This change will spread
throughout the sample if the gray green material is not isolated from the remaining red material.
 The color change, oxidation of Cr(II) to Cr(III) is accompanied by a great deal of heat evolution,
sometimes sufficient to crack the watch glass.

6- Transfer to a pre-weighed sample tube and seal tightly. Weigh the product and calculate the
percentage yield.

Characterization
A sample of chromium(II) acetate properly sealed in a sample tube will remain brick red
indefinitely. However, if exposed to air, it will gradually turn to grey-green color characteristic
of the oxidized material.

Pure [Cr(OAc)2]2.2H2O is diamagnetic because of electron-electron interaction between two

Cr(II) atoms in the dimeric molecule. Any paramagnetism in the sample is indicative of impurity.
The structure of the compound is:

Carry out the magnetic susceptibility measurement to check for purity of the product and record its
melting point and its I.R spectra.

Questions
1. Why chromium(II) is sensitive to air, and why Cr(III) compounds are more stable than Cr(II)
compounds?
2. What is the expected magnetic moment for chromium(II) acetate if it is monomeric?
 Experiment 8

Cu(II) acetylacetonato complex

In this experiment Cu(II) acetylacetonato complex will be prepared and characterized, its visible
spectrum will be closely examined.

Reagent Required
Acetylacetone, 11 mL
Sodium hydroxide, 4.0 g
95% ethanol, 250 mL.
Copper sulfate pentahydrate,11.9 g
Pyridine, 5.0 mL

Experimental Procedures:

1. Dissolve acetylacetone (11 g) in 1.0 M sodium hydroxide solution (4.0 g NaOH in 100 mL
water). Add further acetylacetone drop by drop until a drop remains undissolved, and then just
add enough ethanol to dissolve it. Add to this solution, with stirring, a solution of copper
sulfate pentahydrate (11.9 g in 50 mL water).

2. Filter the precipitate on Büchner funnel, dry it in air (not in the oven) and recrystallize from hot
ethanol (~200 mL).

3. Dry the product in air or in an oven at temperature less than 60oC. Weigh the product and
calculate the percentage yield.

5. Record the melting point of the com[pound, visible spectra in acetone its I.R. spectrum
and its magnetic properties, measure the conductance of the of the compounds in acetone and
determine the molecular weight by freezing point depression method(as in exp1).

Questions

1. From I.R. spectrum and molecular weight determination can you conclude whether the complex
contains coordinated water molecules. Explain.

2. Examine the visible spectrum of the complex, from its extinction coefficient can you decide
The structure of the complex? Explain.
3. Do you notice any Jahn-Teller distortion effect on the visible spectrum of the complex?
Explain.
 Experiment 9
K3[Fe(ox)3]. 3H2O

Oxalate anion, C2O42- forms stable complexes with various metals. In most cases it makes 5-
membered rings with metal ions and binds metal through two oxygen atoms. In this experiment
the complex K3[Fe(ox)3]. 3H2O will be prepared directly from ferric hydroxide , oxalic acid, and
potassium oxalate.

Reagents:

Fe(NO3)3.9 H2O ,12.12 g.

Oxalic acid dihydrate, 5.72g
Potassium oxalate monohydrate, 8.29 g
Conc. ammonia solution.

Experimental Procedures:

1. Dissolve 12.12 g Fe(NO3)3.9 H2O in minimum volume of hot distilled water in 250 mL
Erlenmeyer flask add conc. ammonia solution drop wise until the solution is basic to litmus.
Heat the mixture in hot water bath for 10 minutes and use Buchner funnel to filter the dark
brown ferric hydroxide precipitate, wash the precipitate with water twice.

2. Transfer the wet ferric hydroxide into a 400 mL beaker, use minimum amount of water from
wash to help transfer the precipitate.

3. Add 5.72 g oxalic acid dehydrate and 8.29 g potassium oxalate monohydrate to the ferric
hydroxide mixture add water to a volume of about 100 mL and boil the mixture for 15 minutes.
( you can use direct flame or hot plate). If the mixture does not become clear add small amount
of oxalic acid to boiling mixture(less than one gram) and keep boiling until the mixture become
clear and color turns light green.

4. Keep the solution boiling to reduce volume to about 50 mL., allow solutions to cool to room
temperature and then cool in an ice bathe for 30 minutes.

5. Filter the green crystalline product, wash with 5 mL of cold water and then with 20 mL ethanol
and dry in air.

6. Weigh the product and calculate the % yield.

7. Record the melting point of the complex, its visible spectrum in water, its I.R. spectrum and its
magnetic properties, measure the conductance of the of the complex in 10-3 M aqueous solution.
Questions

1. Examine the visible spectrum of the complex, from its extinction coefficient can you decide
whether the transitions are d-d or charge transfer transitions?

2. Can you conclude whether the complex is tris or bis(oxalato) from the conductance
measurements? How?

3. Examine the IR spectra of the complex and those of the ligand, and conclude the mode of
bonding of oxalate ion in the complex.

4. You noticed that the reactions you carried out in this experiment are fast, explain.

5. In this experiment Fe(OH)3 is reacted with oxalic acid while Cr(OH)3 does not react, explain.
 Magnetic Measurements

1. Clean a Gouy tube by washing it with suitable cleaning solution, distilled water and
acetone. Dry the tube by blowing air through.
2. With magnetic field off, suspend the Gouy tube from the hock on the bottom of the chain
suspending from the balance.
3. Weigh the tube and record the mass m1 (in g).
4. Turn on the magnetic field:
a) Open water valve be sure water is running.
b) Turn on the main switch
c) Turn the second switch and increase the current until its value lies in the range( or
current of 6.0 A)

5. Weigh the tube while magnetic field is on, m2 (in g), turn off the magnetic field, (step 4 in
reverse order) and remove the tube.

6. Finely powder 2-3 g of CuSO4.5H2O in a mortar. Add small portion of CuSO4.5H2O to the
tube; tap the tube firmly on a paper-covered wood surface, until the powder will not push
down any further. Add more powder and repeat until the mark on the tube is reached. At least
ten packings are necessary.

7. Suspend the tube, and weight with magnetic field off, m3 (in g).

8. Turn on the magnetic field and weigh again m4 (in g), record the temperature.

9. Empty the tube, wash it with water, and fill it with water to the mark, weigh again m5 (in g.)

Calibration constants for the tube α and β are determined as follows:

a) α = 0.029 x mass of water(in g). (Mass of water in g = volume of tube in cm3)

= 0.029 x (m5-m1)
6
b) 10 χg =(α+βF’)/W
6
For CuSO4.5H2O , 10 χ g = 5.90 at 20ºC and for HgCo(SCN)4 =16.44, in this lab we will use
the copper (II) sulphate pentahydrate as standard.
Since Curie law is obeyed, χ g α 1/T
6
So χ g for 10 χ g for CuSO4.5H2O at 25oC ,for example, = 5.90x293/298.
 6
In above equation, 10 χg =(α+βF’)/W :
F’ : corrected force = F – Σ(in mg)
Σ: diamagnetic correction for the tube = m2 – m1 ( always negative)
F ; m4 – m3 in mg)
(Since Σ is negative, F’ is always greater than F )
W( mass of the sample) = m3-m1 ( in g)
6
Calculate β for the tube using the formula: 10 χ=(α+βF’)/W
Be careful with the tube, a new tube means new calibration
To obtain the susceptibility of the complex, repeat steps 6-8 , using your complex instead
of CuSO4.5H2O.
Mass of empty tube = m1(as above)( in g)
Mass of empty tube + complex( magnetic field off) = m6( in g)
Mass of empty tube + complex( magnetic field on) = m7( in g)

1-Calculate F (in mg) = 1000(m7 - m6 )

2- Calculate corrected force F’( in mg) = F-Σ( remember Σ has –ve value)
3- Calculate W( in g) = m6 - m1
6
4- Calculate 10 χg = =(α+βF’)/W
5- Calculate χM = χg x (molar mass)
6- Calculate χM' = χm- Δ( sum of diamagnetism, remember Δ has –ve value)
7- Calculate µ= 2.828 √( χM’T), same T in Kelvin as above (recorded by thermometer)

Diamagnetic Susceptibilities(x 106 cgs units) mol-1, Pascal's constants

Cations:
Na+ - 6.8 ; K+ - 14.9 ;Hg2+ -40.0,
Inner core diamagnetism of the first-raw transition metals is about -13 x 10-6 (cgs) mol-1.
Anions:
Cl- -23.4 ; Br- -34.6 ; NO3- -30.2
Some ligand:
H2 O -13; NH3 -18 ; CH3COO- -30 ; NH2CH2CH2NH2 -46
C2O42- -25 ; acetylacetone -52 ; pyridine -49
Neutral atoms:
H -2.93 ; C -6.00 ; N(ring) -4.61 ; N(open chain) -5.57 ; N( imide) -2.11
O( ether or alcohol) - 4.61 ; O( aldehyde or ketone) -1.73 ;S -15.0.
Constitutive Corrections:
C=C +5.5 ; N=N +1.8 ; C(in benzene ring) +0.24 ; C=N-R +8.2 ;
C=C-C=C 10.5
 Electrical Conductance

The resistance, R in ohms, of a solution is directly proportional to the distance between the
two electrodes and inversely proportional to the electrodes area.
R = ƍ . d/A
Where ƍ is the specific resistance or resistivity in ohm.cm.( The resistance of a solution
measured with a cell that has one cm2 area and separated by one cm).
d/A is called the cell constant, k.
R = ƍ . d/A = ƍ . k or ƍ=R/k
The conductance of a solution, C = 1/R in ohm-1 or Siemens (s) units.
So, C = 1/R = A/ ƍ . d = L / k.
Where L = 1 / ƍ = k /R = k . C
L is called specific conductance, in ohm-1 cm-1 units.
The cell constant, k, is obtained for any cell by measuring the electrical conductance of
0.02000 M KCl solution at 25 oC. The specific conductance, L of this solution is
0.002768 ohm-1.cm-1.
The molar conductance , ΛM is defined as:
ΛM = 1000 L/M ( in ohm-1 mol-1 cm2 or s. mol-1 cm2 which is the conductance of 1cm3 of
a solution that contains one mole of electrolyte.
The values of ΛM at 25 oC and about 10-3 M solution are given for simple electrolytes, the values
for complex ions may lie slightly out of the given ranges but the given table is good enough
guideline to distinguish between 1:1 2:1 and 3:1 electrolytes.

Solvent dielectric constant 1:1 2:1 3:1

Water 78.4 118-131 235- 273 408 435

Nitromethane 35.9 75-95 150-180 220-260
Acetone 20.7 100-114 160-200
Methanol 32.6 80-115 160-220
 References

1.Bailar, J. C., Jones, E.M. (1939) Inorg. Synth., 1, 37.

2.Charles, R.G. (1963) Inorganic Synthesis 7, 183-184.
3.Collman, J.P. (1965). Angew. Chem. Int. Ed. 4, 132-138.
4.Collman, J.P. Goldby, S., Young, W.L. III & Marshall, R. (1962). Inorg. Chem. 1, 704-710.
5.Collman, J.P., Young, W.L. III & Kauffman, G.B. (1963). Inorg. Synth. 7, 205-207.
6.Combes, C.R., (1890). Acad. Sci., iii 272.
7.Goodgame, D.M.L. et. al, (1965), Inorg. Chem. 4, 823.
8.Schirado, T., Gennari, E. Merello, R., Decinti, A. & Bunel, S. (1971). J. Inorg. Nucl. Chem. 33, 3417-
3426.
9. Werner, A., (1913).
10. Szafran,Zvi;Pike,R.M and Singh,M,M,Wiley(1991).