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Synthesis of Metal Acetylacetonate Complexes
Synthesis of Metal Acetylacetonate

Background. In this experiment you will prepare and characterize complexes of 2 metal ions
with the anion of acetylacetone. Acetylacetone (2,4-pentanedione) is a typical o-diketone that
can ionize in aqueous solution as a weak acid:

The resulting acetylacetonate anion (abb. acac) can serve as a ligand to metal ions, forming
complexes in which the ligand is bonded to the metal through both oxygen atoms to form a six-
membered ring.
The six-membered rings (MO2C3) are planar and weakly aromatic because they contain
6 t electrons. In complexes of stoichiometry M(acac)3, the MO6 array is octahedral; in Cu(acac)2,
the CuO4 group is square planar; and in VO(acac)2, the VO5 group is square pyramidal. In general
the complexes are neutral and may be isolated as crystalline solids having an interesting variety
of colors.
In pure acetylacetone, or solutions of acetylacetone in non-polar organic solvents, the diketo
form is in equilibrium with a cyclic enol-like form. This second tautomer may be regarded as a
complex in which the proton takes the role of the metal ion M
Synthesis and Characterization of Metal Acetylacetonates
Synthetic Procedures
We would like you to carry out syntheses of two metal acetylacetonate complexes, according to
the following plan:
a. Al
and Cr

b. Fe
+, Co

c. Co
, and the nitration of the Co

Characterization of Products
1. In the case you carry out a.: determine the melting points of your 2 products. Next, record
the IR spectrum, using the KBr pellet technique. Label and number the spectra and assign
the "sore thumb" bands. Finally, measure the magnetic susceptibility.
2. In the case you carry out b.: determine the melting points of your 2 products. Next, record
the IR spectrum, using the KBr pellet technique. Label and number the spectra and assign
the "sore thumb" bands. Finally, measure the magnetic susceptibility.
3. In the case you carry out c.: determine the melting points of your 2 products. Next, record
the IR spectrum, using the KBr pellet technique. Label and number the spectra and assign
the "sore thumb" bands. Finally, measure the
H nuclear magnetic resonance (NMR),
using CDCl3 as the solvent and TMS as the reference. Label and number the spectra.

Give a reaction mechanism for the formation of the acatylacetone complexes. Explain the
magnetic behaviour measured in experiment a and b.
Try to give an reaction mechanism for the nitration of Co(acac)3.
In case you carry out experiment c., do you think it is useful to measure the magnetic
1. R.C. Young, Inorganic Syntheses, 2, 25(1946). Al(acac)3.
2. R.A. Rowe, M.M. Jones, Inorganic Syntheses, 5, 114(1957). VO(acac)2.
3. W.C. Fernelius, J.E. Blanch, Inorganic Syntheses, 5, 130(1957). Cr(acac)3.
4. R.G. Charles, Inorganic Syntheses, 7, 183(1963). Mn(acac)3.
5. B.E. Bryant, W.C. Fernelius, Inorganic Syntheses, 5, 188(1957). Co(acac)3.
6. J.B. Ellern, R.O. Ragsdale, Inorganic Syntheses, 11, 83(1968). Co(acac)2(H2O)2.
7. C. Glidewell, J.S. McKechnie, J. Chem. Ed., 65, 1015(1988).
8. D.W. Barnum, J. Inorg. Nucl. Chem., 21, 221(1961). Electronic Absorption Spectra of
metal acac complexes.
9. K. Nakamoto, P.J. McCarthy, A. Ruby, A.E. Martell, J. Amer. Chem. Soc., 83,
1066(1961). A discussion of IR spectra of some trivalent metal acac complexes.
10. K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Compounds,
4th ed., Wiley, New York, 1986. An advanced reference with data for many metal
complexes, including metal acacs.

Synthetic Procedures for Metal Acetylacetonate Complexes
Weigh 0.33 g acetylacetone into a small Erlenmeyer flask. Add 4 mL distilled water followed by
0.8 mL of 5M NH3.
Dissolve 0.3 g of aluminum sulphate, Al2(SO4)3.16H2O,in 3 mL of distilled water. Add the
ammoniacal solution of acetylacetone to the aluminum sulfate solution in small portions, with
swirling. After complete addition of acetylacetone solution, check the pH using blue litmus paper.
If the solution is still acidic, add 5M ammonia dropwise until it is just basic. Let stand for 15
Filter the product, wash with 10 mL of distilled water, and dry by suction for 10 minutes.
Transfer the product to a watch glass and air dry. Determine the % yield.
Recrystallize a portion of your sample from cyclohexane. Isolate the resulting crystals by suction
filtration, wash with a small volume of cold cyclohexane, and suction dry for 15 minutes. Then
let dry thoroughly in air.

Place 5 mL distilled water in a 50-mL round bottom flask, and slowly add an equal volume of
concentrated H2SO4. Add 12 mL ethanol followed by 2.5 g of vanadium pentoxide, V2O5. Attach
a water cooled condenser to the flask and reflux the mixture for about 1.5 hours. Then cool the
mixture under the tap, and gravity filter. Discard any solid residue.
To one-sixth of the filtrate, add 1 mL acetylacetone dropwise with swirling. Neutralize the
mixture by adding it carefully to a solution of 3.3 g of anhydrous Na2CO3 in 25 mL distilled
water contained in a 50 mL Erlenmeyer. Swirl continuously. Cool the resulting mixture in an ice
bath for 15 minutes, then suction filter. Wash the product with cold distilled water (2 * 1.5 mL).
Suction dry for 15 minutes, then transfer to a watch glass and air dry. Determine % yield.
To recrystallize, dissolve about 0.5 g of the crude, dry product in 6 mL of dichloromethane, and
gravity filter the mixture to remove residue. Add 20 mL of petroleum ether, swirl, and allow to
stand for 10 minutes. Isolate the product by suction filtration and wash with cold pet ether.
Suction dry.

Into a 25-mL Erlenmeyer, weigh 0.22 g of chromium(III) chloride hexahydrate and add 8 mL of
distilled water. Swirl to dissolve. Add 1.5 g of urea in 3 or 4 portions to the chromium chloride
solution, swirling well after each addition. Then add 0.47 g of acetylacetone using a Pasteur pipet.
Swirl the mixture, cover it with a watch glass, and heat vigorously on a steam bath for 1.5 hour.
Cool the reaction mixture and isolate the product by vacuum filtration. Dry the crude product in
In a 25-mL Erlenmeyer, place 0.2 g of crude product and 20 mL of cyclohexane. Cover the flask
with a watch glass and heat to boiling on a steam bath. Boil 4-5 minutes with frequent swirling.
Remove from the steam bath, allow to settle for 30 seconds, then decant the solution into a clean
100-mL Erlenmeyer, leaving any solid residue behind. Add 2 mL cyclohexane, reheat to boiling,
and cool slowly to room temperature, leaving the flask covered with a watch glass. Isolate the
product by suction filtration, suction dry, then air dry.

Dissolve 0.26 g manganese(II) chloride tetrahydrate and 0.68 g of sodium acetate in 10 mL of
distilled water. Add 1 g acetylacetone and swirl the mixture. With magnetic stirring, add
dropwise a solution of 0.052 g potassium permanganate in 2.5 mL of distilled water over a
period of 10-15 minutes. Stir for 10 minutes, then add dropwise a solution of 0.63 g sodium
acetate in 2.5 mL distilled water. Heat the resulting mixture on a hot plate to between 60 and
C for 15 minutes, with stirring, then cool to room temperature. Isolate the product by suction
filtration and wash it with 6.0 mL of cold distilled water. Suction dry for 15 minutes, then dry in
air. Determine % yield.
Recrystallize about 0.2 g of the crude product as follows. Place the product in a 25 mL
Erlenmeyer, and add 12 mL of cyclohexane. Place a small glass funnel in the mouth of the flask
and boil on a steam bath for 1 minute. Let the mixture settle for 1 minute, then carefully decant
the solution from the solid residue into a 100 mL Erlenmeyer. Reheat for 1 minute to redissolve,
then add 40 mL of petroleum ether. Swirl, and cool slowly to room temperature, then in an ice
bath. Isolate the product by suction filtration and wash with 10 mL of cold pet ether. Dry by
suction for 15 minutes, then air dry.
Dissolve 0.33 g of finely-ground iron(III) chloride hexahydrate in 2.5 mL of distilled water. Over
a period of 15 minutes, add a solution of 0.38 g of acetylacetone in 10 mL methanol, with
constant magnetic stirring. To the resulting mixture, add, over a period of 5 minutes, a solution
of 0.51 g of sodium acetate dissolved in 1.5 mL of distilled water, maintaining stirring
throughout. Heat the mixture rapidly to about 80
C using a hot plate and maintain at this
temperature for 15 minutes, with rapid stirring. Cool to room temperature, then in an ice bath.
Isolate the product by suction filtration and wash with 10 mL of cold distilled water. Suction dry
for 15 minutes, then air dry. Determine % yield.
Place 0.2 g of the crude product into a 25-mL Erlenmeyer, and add 3 mL of distilled water.
Warm on a steambath and add methanol dropwise, maintaining gentle heating, until the crude
product just dissolves. Cool in an ice bath for 15-30 minutes. Isolate the product by suction
filtration, suction dry for 15 minutes, then air dry.

A mixture of 2.5 g CoCO3 and 20 ml. of acetylacetone is heated with a steam bath to
approximately 85
C. When 30 ml of 10% H2O2 is added drop wise to the mixture it becomes
green in color. When effervescence ceases, the reaction is complete. The flask is chilled in an
ice-salt bath and is vacuum filtered. The product is then washed with cold ethanol and then air-
dried. Dissolve Co(acac)3 in boiling toluene ( 50 ml ) , filter if necessary , then add about 70 ml
of heptanes and cool in an ice bath to precipitate the product. Filter the sample, air dray for a few
minutes. Determine % yield.

Copper nitrate trihydrate (2.6 g) is cruched and added to 40 ml of acetic anhydride in a dry flask.
Co(acac)3 (1.0 g) is then added to the mixture; the flask is stopped and the mixture is stirred
vigorously at room temperature for 30 min. The mixture is poured into a baker containing 120 ml
of water, sodium acetate (3 g), and 120 g of ice. It is stirred vigorously. Then the product usually
separates as an oil. To solidify the oil, add ethanol and stir vigorously. Then the product can be
filtered, washed with 5 ml ethanol, and recrystalized from metylenechloride-ethanol ( dissolve in
as little as possible methylenechloride an add so much ethanol that de product just precipitates)

Dissolve 0.4 g of copper(II) chloride dihydrate in 2.5 mL of distilled water in a 25 mL
Erlenmeyer. Over a period of 20 minutes, add dropwise a solution of 0.5 mL of acetylacetone in
1 mL methanol, with constant stirring. To the resulting mixture, add 0.68 g of sodium acetate
dissolved in 1.5 mL of distilled water over a period of 5 minutes. Heat the mixture to about 80
on a hot plate for 15 minutes, maintaining rapid stirring. Cool to room temperature, then in an ice
bath. Isolate the product by suction filtration, wash with 10 mL of cold distilled water, and
suction dry for 15 minutes. Air dry thoroughly, and determine % yield.
Place about 0.2 g of crude product in a 100 mL Erlenmeyer, and add 25 mL methanol. Place a
small glass funnel in the mouth of the flask to serve as a reflux condenser, and boil on a steam
bath for 5 minutes. Carefully decant the solution into a 100 mL Erlenmeyer, leaving any solid
residue behind, and add 5 mL of methanol. Reheat to dissolve, then cool to room temperature.
Isolate the product by suction filtration. Wash with a little ice-cold methanol, and suction dry,
then air dry.

To a solution of 80 mg NaOH in 1 mL H2O, slowly add 200 mg (2 mmole) acetylacetone, with
swirling. Any white solid formed at this point must be dissolved before continuing. This yellow
solution is added dropwise, with stirring, to a solution of 238 mg (1 mmole) CoCl2.6H2O in 1.5
mL of water. Isolate the product by suction filtration and wash with water until the washings are
nearly colorless (2-5 mL). Suck dry for 10 minutes, then air dry for a further hour. Weigh the
product and calculate %yield.
Dissolve the crude product in a hot mixture of 2 mL ethanol and 1.3 mL chloroform (do not boil
the resulting solution). Gravity filter through a Kimwipe plug in a Pasteur pipet. Cool the filtrate
slowly to room temperature, then cool further in an ice bath. Isolate the product by suction
filtration, wash with cold ethanol/H2O (20/1 v/v), and suck dry.


Synthesis of a Molybdenum Sulfur Complex
Synthesis of a Molybdenum Sulfur Complex

Background. Metals of the d block of the periodic table are extremely important components of
many proteins and enzymes. Chemists are interested in the synthesis of complexes of these
metals that have simple structures, yet imitate either the structure or function of the active sites
of these proteins. A problem of long-standing interest in inorganic chemistry is that of finding a
way to "fix" nitrogen (convert N2 from the air into NH3 that is usable as fertilizer), a process that
is currently done commercially using the energy-intensive Haber process. We have yet to
discover how certain bacterial are able to take N2 from the air under ambient conditions and
convert it to NH3. The enzyme that accomplishes catalysis of this process is called nitrogenase.
Nitrogenase contains a molybdenum ion and several iron ions at the active site, bound by sulfur
donor ligands. It has thus been of interest to create laboratory molecules that feature Mo in a
sulfur-rich context, and bind N2 to that. In this experiment, you will synthesize and characterize a
molybdenum complex containing sulfur ligands: MoO2(Et2dtc)2, where Et2dtc is the abbrevation
for the ligand, bis-N,N-diethyldithiocarbamato anion. The structure of the complex is shown

Procedure for Synthesis of cis-Mo
O2(S2CNEt2)2.(Method A ) Add 10 mmole Na2MoO4.2H2O
and 20 mmole Na(S2CNEt2).3H2O to 35 mL of water in a 250-mL Erlenmeyer flask containing a
magnetic stirring bar. Stir to dissolve the solids, then add 35 mL of ethanol. Dilute 4 mL of
concentrated HCl to 100 mL with distilled water. REMEMBER TO ADD ACID TO WATER,
NOT THE REVERSE. While stirring vigorously, add the HCl solution DROPWISE to the
molybdate/dithiocarbamate mixture over a period of 10-15 minutes. NOTE: SLOW ADDITION
OF THE HCl IS IMPORTANT. Isolate the product by suction filtration, wash with 1:1
water/ethanol, and suction dry. Recrystallize from dichloromethane/petroleum ether.
IR ( KBr ) (CN) 1510 s; (Mo=O) 920, 880 s cm
H NMR (CDCl3, 400 MHz: 1.32 ( t, 12H
J 7.5 Hz, 4 x CH3),
3.80 ( q, 8H, 4x CH2)

Procedure for Synthesis of cis-Mo
O2(S2CNEt2)2.(Method B ) Success depends on vigorous
agitation or magnetic stirring during the addition of the hydrochloric acid. Diethylamine ( 2.4 ml,
23 mmol ) and sodium hydroxide ( 0.9g, 23 mmol ) are added to water ( 50 ml ) in a 250-ml
Erlenmeyer flask. After stirring for 5 min, the mixture is treated with carbon disulfide ( 1.4 ml,
23 mmol ), a watch glass is placed over the top of the flask and the solution is stirred for a further
10 min. Sodium molybdate(VI) dihydrate ( 3.5g, 14.5mmol ) is added to the mixture, which is
then treated drop wise ( from a dropping funnel, over about a 10 min period ) with a solution of
6ml concentrated hydrochloric acid in water ( 100ml ). Vigorous stirring is required during the
drop wise addition; the dense yellow-brown product precipitates. The solid is isolated by vacuum
filtration, washed well with water ( 60ml ) , ethanol ( 60ml ), then ether ( 60 ml ) and dried at the
pump. The crude material may be employed in the synthesis that follows. The remaining of the
sample can be recrystallized by dissolving it in dichloromethane ( 15 ml/g ), filtering, and adding
ether ( 20ml/g ) to the clear filtrate. Yield 4.0g, 85%

IR ( KBr ) (CN) 1510 s; (Mo=O) 920, 880 s cm
H NMR (CDCl3, 400 MHz: 1.32 ( t, 12H
J 7.5 Hz, 4 x CH3),
3.80 ( q, 8H, 4x CH2)

Procedure for Synthesis of Mo
O(S2CNEt2)2.This compound is moderately air-sensitive and all
work should be preformed quickly and efficient. In a small round-bottomed flask connected with
a water or air condenser, a mixture of cis-Mo
O2(S2CNEt2)2 (1.0 g, 2.3 mmol ) and
triphenylphosphine ( 1.0 g, 3.8 mmol; the excess allows the synthesis to be preformed in air ) in
1,2-dichloreethane (bp. 82
C, 10 ml ) is refluxed for 10-15 min. Ensure that reflux ( in a
preheated bath ) is commenced immediately after adding the solvent to the starting materials.
Upon completion of the reflux pour the reaction mixture, with swirling, in to ice-cold ethanol
( 50 ml ) contained in a 100-ml Erlenmeyer flask. Filter the crystals, wash with ethanol, then
ether, and vacuum dray. Yield 0.77g, 80%

IR ( KBr ) (CN) 1520 s; (Mo=O) 960 s cm
H NMR (CDCl3, 400 MHz: 1.35 ( t, 12H
J 7.5 Hz, 4 x CH3) 1.87
and 3.93 ( m, 8H
J 15 Hz,
J 7.5 Hz, 4 x diasteriotopic CH2

Characterization. Characterize the product using appropriate physical methods.

1. FW Moore, ML Larson, Inorg. Chem., 1967, 6, 998.
2. CG Young, J. Chem. Ed., 1995, 72, 751.

Cobaloximes - Models for Vitamin B12
Cobaloximes - Models for Vitamin B12

Since the discovery in 1948 that Co was an essential part of Vitamin B12, the isolation, structural
determination and synthesis of the vitamin have been accomplished and the final pieces of it's
biosynthetic pathway are nearly completed. This is a remarkable achievement considering that
per cm
of blood there is only about 10
g of vitamin B12 found!
However, the role of the vitamin is not yet fully understood, although it is known that it is
essential in preventing the disease pernicious anaemia.
Three biologically active cobalamins can be detected in the serum and tissues of man and higher
animals, these are: adenosylcobalamin, AdoCbl; hydroxocobalamin, OH-Cbl; and methyl-
cobalamin, MeCbl. Cyanocobalamin, CN-Cbl has been detected in chromatograms of the blood
of smokers, where it is believed to be formed from HCN from cigarettes reacting with OH-Cbl. It
has no physiological role (apart from this unexpected detoxification of cyanide) although it has
been used for treating pernicious anaemia because like OH-Cbl, it can be converted in vivo into
Ado-Cbl and MeCbl.
Pernicious anaemia is largely a disease affecting people over the age of 40 and is almost
unknown in negroes. In the UK, it occurs with a frequency of 1 in 1000. The consequence of
depriving people of essential cobalamins is debilitation which if continued can end in death.
The model compound to be prepared in this experiment contains an ethyl-cobalt bond. The
cobaloximes have been used as models due to their ease of preparation, purification and

Preparation of bis(dimethylglyoxime)ethylpyridinecobalt(III)


A 250 cm
three necked flask is equipped with a pressure equalising dropping funnel which in
turn is attached to a gas outlet bubbler. The central neck is stoppered and the third neck is
equipped with an inlet to bubble nitrogen gas through the reactants. This enables the system to be
deoxygenated and allows the later stages of the experiment to be conducted with strict exclusion
of oxygen. A mixture of methanol (100 cm
) and pyridine (0.8 g, 11mmol) is magnetically stirred
under nitrogen flow for several minutes.

Carefully remove the stopper briefly (increase the gas flow momentarily) then dimethylglyoxime
(2.32 g, 20 mmol) is added, followed by finely powdered cobalt(II) chloride hexahydrate (2.37 g,
10 mmol). Not all the reactants will dissolve but the deep brown colouration due to the Co(II)
complex should appear. Sodium hydroxide (1.6 g, 40 mmol) dissolved in the minimum amount
of water (about 5 cm
) is added via the dropping funnel. The intense blue-black colour of the
cobalt(I) intermediate should develop over the next 2-4 minutes. If it does not then air has
attacked the cobalt(I) intermediate and the experiment should be repeated.
Next, a solution of iodoethane (0.78 g, 5 mmol) dissolved in a little methanol (about 5 cm
) is
added, again via the dropping funnel. The organocobaloxime forms immediately as evidenced by
the blue suspension turning brown. The methanol solvent is removed by rotary evaporation at
about 50
C ( higher temperatures may lead to decomposition ). The pasty mass is stirred with a
slush of ice and water (about 200 cm
). This oxygenates and solubilises the unwanted by-
products but does not significantly decrease the yield of product.
The orange brown cobalt complex is filtered on a sintered glass funnel and washed with 100
of ice-cold water. Dry in a dessicator in the dark (the product is somewhat light sensitive)
and record the yield.

Alternative synthesis.

Synthesis of Dibromo(dimethylglyoxime)dimethylglyoxomatocobalt(III). Dimethylglyoxime
( 2.20g, 19.0 mmol ) was added to a stirred solution of 3.00 g cobalt(II)bromide hydrate ( 9.17
mmol ) in 50 ml of aceton. As a very gentle stream of air was placed over the solution a green
solid was deposited. After 30 min, the solution was chilled on ice, filtered, and washed with 2 x
15 ml of cold acetone. The yield of green microcrystalline product was 3.5- 3.9g ( 85-95% yield
based on CoBr2). The compound has very low solubility and was therefore not characterized

Synthesis of Bromo(4-tert-butylpyridine)cobaloxamine.
A quantity of 3.5g (7.78 mmol ) of the green product (1) was suspended in 80 ml of methanol
and 2.20g ( 2.42 ml, 16.3 mmol ) of 4-tert-butylpyridine was added. The mixture was stirred
until the green solid had disappeared and was replaced by a brown crystalline solid ( 20-30 min ).
Water ( 125 ml ) was added with stirring and the suspension was cooled in ice for 10 min. The
product was collected by suction filtration and washed with 3x15 ml of 2:1 water/methanol and
2x10 ml of diethyl ether. The yield of the brown microcrystalline solid was about 3.5g (89% ).

Systhesis of Ethyl(4-tert-butylpirydine)cobaloxine.
Three or four KOH pellets are disolved in 40 ml of methanol in a 200-ml two-neck flask and
1.50g ( 3.00 mmol ) of (2) was added. The homogeneous mixture was chilled in a ice/salt bath
( to about 10
C ) and was thoroughly deaerated with nitrogen bubbeling (~10 min ). Sodium
borohydride ( 0.15g, 3.9 mmol ) was added ( carefully ) against a positive nitrogen flow and the
mixture rapidly turned dark blue-green. The solutuion was stirred for 5 min and 0.50 ml (0.98g,
6.3 mmol ) of ethyl iodide was added via graduated pipet (against a positive nitrogen flow ). The
mixture immediately turned red-brown and was stirred in the ice bath for 20 to 30 min. The
reaction was quenched by the addition of acetone (5 ml ) and water (60 ml ). The volume was
reduced to 50 ml on a rotary evaporator and an orange crystalline solid was deposited. The flesk
was chilled in a ice bath and the orange solid was filtered and washed with water. The yield for
this step was 1.0-1.2g (73-88% ) The compound was sufficiently pure as judged by NMR, but it
may be recrystallized by dissolving in methanol, adding an equal volume of water, and reducing
to half volume on a rotary evaporator.

1H NMR Spectocopic data for Cobaloxime Derivatives, Co(dmgH)2(4-t-BuPy)X
X Oxime


O-H-O Ethyl
Br 2.40
ca 17.5
- -
Et 2.13
ca 17.5
Solvent CDCl3

1) Compare the yields of the two different syntheses.

B. T. Golding, Chem. in Britain, 26, 1990, 950.
Hill et al., J. Chem. Soc (A), 1969, 554.
R.H. Abeles and D. Dolphin, Accounts Chem. Res., 9, 1976, 114.
Comprehensive Organometallic Chemistry, Ed G. Wilkinson, Pergamon Press, 1984.vol 5.

Infrared Spectroscopy
Infrared Spectroscopy
When a beam of electromagnetic radiation of intensity I
is passed through a substance, it can
either be absorbed or transmitted, depending upon its frequency, and the structure of the
molecule it encounters. Electromagnetic radiation is energy and hence when a molecule absorbs
radiation it gains energy as it undergoes a quantum transition from one energy state (Einitial) to
another (Efinal). The frequency of the absorbed radiation is related to the energy of the transition by
Planck's law: Efinal - Einitial = E = hv = hc/ . Thus, if a transition exists which is related to the
frequency of the incident radiation by Planck's constant, then the radiation can be absorbed.
Conversely, if the frequency does not satisfy the Planck expression, then the radiation will be
transmitted. A plot of the frequency of the incident radiation vs. some measure of the percent
radiation absorbed by the sample is the absorption spectrum of the compound.

The type of absorption spectroscopy depends upon the type of transition involved and
accordingly the frequency range of the electromagnetic radiation absorbed. If absorption is
accompanied by a transition from one rotational energy level to another then the radiation is
from the microwave portion of the electromagnetic spectrum and the technique is microwave
spectroscopy. If the transition is from one vibrational energy level to another, then the radiation
is from the infrared portion of the electromagnetic spectrum and the technique is known as
infrared spectroscopy. If the transition alters the configuration of the valence electrons in the
molecule, then the radiation is from the ultraviolet-visible portion of the spectrum and the
technique is ultraviolet-visible, or electronic absorption, spectroscopy.
Infrared Spectroscopy
There are in general several types of motion that a molecule may undergo. First, the molecule as
a whole may move through space in some arbitrary direction and with a particular velocity. This
type of motion is called translational motion and with it we associate the translational kinetic
energy of the molecule, given by mv
/2 (v = velocity of the center of mass of the molecule). The
velocity with which a molecule translates may be resolved into components along each of the
three axes of a Cartesian coordinate system, so that we may write mv
/2 = mvx
/2 + mvy
/2 +
/2, where vx is the x-component of velocity, etc., and m is the mass of the molecule. This
equation tells us that we may consider the total translational KE of the molecule to be made up of
three parts, each of which represents the kinetic energy of the molecule along one of the
reference directions. Since any translation of the molecule may be considered to arise from the
vector sum of its motions along the three axes, the kinetic energy may always be broken up into
the sum of three contributions, one arising from motion along the x axis, one from motion along
the y axis, and one from motion along the z axis. We characterize this situation by saying that the
molecule has 3 translational degrees of freedom, one corresponding to each Cartesian axis.
Second, the molecule may rotate about some internal axis. Again, any such axis may be resolved
into components along the x, y, and z axes of a Cartesian coordinate system, so that any rotation
of the molecule may be resolved into three mutually perpendicular components. The rotational
kinetic energy of the molecule can then be written
KErot = Ixex
/2 + Iyey
/2 + Izez
where Ix, Iy, and Iz are the moments of inertia about the x, y, and z axes, and x, y, and z are the
angular velocities about these axes. Again, then, we see that there are in general 3 degrees of
freedom associated with rotational motion, one corresponding to each Cartesian axis. An
exception to this generalization arises in the case of a linear molecule, for which one of the three
axes is normally taken as the molecular axis. Consider, for example, the diatomic molecule
shown in the figure below. The molecule is shown with its bond axis coincident with the z axis
of a coordinate system. In this case, the molecule

has no rotational energy about the z axis, because the moment of inertia about this axis is zero.
For linear molecules, then, there exist only two rotational degrees of freedom, rather than 3.
Finally, the molecule may vibrate. A diatomic molecule, for example, vibrates by repeated
stretching and contraction of the bond joining the two atoms, as shown below:

Such a molecule has, in addition to 3 translational and 2 rotational degrees of freedom, one
vibrational degree of freedom. In general, for a polyatomic molecule, we may deduce the number
of vibrational degrees of freedom (sometimes called vibrational modes) by subtracting the
number of translational and rotational degrees of freedom from the total number of degrees of
freedom possessed by the molecule. The latter number is simply 3N, where N = the number of
atoms in the molecule. (Realize that each atom may independently move in any of three
directions. Each atom has, therefore, 3 degrees of freedom available to it, for a total of 3N for the
molecule.) This leads us to the general rule, that the number of vibrational degrees of freedom is
given by 3N-6 for a non-linear polyatomic molecule; and by 3N-5 for a linear polyatomic
molecule. According to this rule, the water molecule, which is a non-linear molecule with N = 3,
should have 3 vibrational degrees of freedom--in other words, should undergo three independent
types of vibration. These are shown below.

The arrows show the directions in which the atoms move during the vibration.
Each of the vibrational motions of a molecule occurs with a certain frequency, which is
characteristic of the molecule and of the particular vibration. The energy involved in a particular
vibration is characterized by the amplitude of the vibration, so that the higher the vibrational
energy, the larger the amplitude of the motion. According to the results of quantum mechanics,
only certain vibrational energies are allowed to the molecule (the same may be said of rotational
and translational energies), and thus only certain amplitudes are allowed. Associated with each
of the vibrational motions of the molecule, there is a series of energy levels (or vibrational
energy states). The molecule may be made to go from one energy level to a higher one by
absorption of a quantum of electromagnetic radiation, such that Efinal-Einitial = hv . In undergoing
such a transition, the molecule gains vibrational energy, and this is manifested in an increase in
the amplitude of the vibration. The frequency of light required to cause a transition for a
particular vibration is equal to the frequency of that vibration, so that we may measure the
vibrational frequencies by measuring the frequencies of light which are absorbed by the
molecule. Since most vibrational motions in molecules occur at frequencies of about 10
then light of wavelength = c/ = 3 x 10
= 3 x 10
cm = 3 microns will be
required to cause transitions. As it happens, light of this wavelength lies in the so-called infrared
region of the spectrum. IR spectroscopy, then, deals with transitions between vibrational energy
levels in molecules, and is therefore also called vibrational spectroscopy. An IR spectrum is
generally displayed as a plot of the energy of the infrared radiation (expressed either in microns
or wavenumbers) versus the percent of light transmitted by the compound. This is indicated
schematically below.

Within this energy range the spectrum of the molecule will appear as a series of broad absorption
bands of variable intensity, each of which brings to the viewer some piece of structural
information. Each absorption band in the spectrum corresponds to a vibrational transition within
the molecule, and gives a measure of the frequency at which the vibration occurs. For the water
molecule, for which there are three vibrational degrees of freedom, there are consequently three
sets of energy levels within which transitions may occur. These are shown below, along with the
particular vibration corresponding to each.

Note that the spacing between energy levels depends upon the particular vibration being
considered. Each spacing requires a photon of different energy to cause the transition, so we
expect photons of three different energies to be absorbed by H2O. This is found to be the case,
the frequencies of the photons (hence of the vibrations) falling at 3500 cm
, 1650 cm
, and 600-
, respectively.
The fact that a molecule vibrates does not in itself insure that the molecule will exhibit an IR
spectrum. In order for a particular vibrational mode to directly absorb infrared electromagnetic
radiation, the vibrational motion associated with that mode must produce a change in the dipole
moment of the molecule. HCl, for example, with a center of positive charge located near the H
atom and a center of negative charge located near the Cl atom, has a dipole moment. Moreover,
the magnitude of the dipole moment will change as the HCl bond stretches, and this vibration
will absorb IR radiation. HCl will exhibit an IR spectrum and is thus termed an infrared active
molecule. The NN molecule, on the other hand, has no dipole moment. Furthermore, stretching
the N-N bond will not produce a change in dipole moment, so this molecule is infrared inactive
(i.e., cannot directly absorb IR radiation). It is important to realize that there are many molecules
which, although possessing no permanent dipole moment, still undergo vibrations which cause
changes in the value of the dipole moment from 0 to some non-zero value. Consider the
CO2 molecule:
This molecule obviously has no permanent dipole moment, since the individual bond dipoles
exactly cancel each other. However, when the molecule undergoes a bending vibration, as shown
below, its dipole moment changes from zero to some non-zero value:

This vibration produces a change in dipole moment and is therefore IR active.
For the vibrations of the water molecule illustrated earlier, a little study will show that all three
types of motion lead to a change in dipole moment. Hence all three vibrations of the water
molecule are IR active and we expect that each will give rise to an absorption band in the IR
region. We have already seen that this expectation is borne out.
The requirement that a vibration must cause a change in the dipole moment of the molecule in
order to absorb radiation can be understood if we realize that exchange of energy between
electromagnetic radiation and matter can occur only if the radiation and matter can interact (or
couple) in some way. Electromagnetic radiation consists of perpendicular electric and magnetic
fields, which oscillate sinuosoidally at the frequency of the radiation. The electric oscillation is
shown as a sine wave below:
Note that this oscillation of the electric field is equivalent to an oscillating dipole moment. Now
a molecule may interact with the radiation by interacting with the oscillating electric field, but
such interaction is possible only if the molecule also possesses an oscillating electric field.
Furthermore, the frequencies of the oscillations must be the same. We therefore see that if a
vibrational motion of a molecule is to absorb IR radiation, the motion must generate an
oscillating electric field. This is equivalent to saying that the vibration must produce a change in
dipole moment. The dipole moment will oscillate at the frequency of the vibration, so that
radiation of this frequency may then be absorbed.
In addition to the number of distinct vibrations to be expected for a given molecule, we can make
certain general statements about where in the spectrum absorptions due to certain types of
vibrations may be expected to occur. It can be shown that, for a diatomic molecule, A-B, the
wavenumber (i.e., the reciprocal of the wavelength) of the infrared radiation absorbed by the
vibration of the molecule is given by
vbar = 1/2t (kAB/AB)
where AB = MAMB/(MA + MB)
Here kAB is the force constant for the bond between A and B, and is a measure of the bond
strength; and MA and MB are the masses of the atoms which are bonded together. We conclude
from this equation that the heavier the atoms involved in the bond, the lower the absorption
frequency should be, given a fairly constant bond strength. We have to be careful in applying this
equation, however. For the series HF, HCl, HBr, and HI, the IR absorptions occur at,
respectively, 3958, 2885, 2559, and 2230 cm
. It is tempting to jump to the quick conclusion that
this is a result of the increase in mass of the halogen atom. Calculation of for each molecule,
however, reveals that the reduced mass actually changes very little. The change in frequency is
actually due to the decrease in bond strength along the series.
Applications of IR Spectroscopy to Organic Molecules
Organic functional groups differ from one another both in the strength of the bond(s) involved,
and in the masses of the atoms involved. For instance, the O-H and C=O functional groups each
contain atoms of different masses connected by bonds of different strengths. According to
equation (1), we therefore expect the O-H and C=O groups to absorb IR radiation at different
positions in the spectrum. The presence of a strong, broad band between 3200 and 3400 cm
indicates the presence of an O-H group in the molecule, while the presence of a strong band
around 1700 cm
confirms the presence of a C=O group.
For organic molecules, the infrared spectrum can be divided into three regions. Absorptions
between 4000 and 1300 cm
are primarily due to specific functional groups and bond types.
Those between 1300 and 909 cm
, the fingerprint region, are primarily due to more complex
interactions in the molecules; and those between 909 and 650 cm
are usually associated with the
presence of benzene rings in the molecule. Some particularly important regions are indicated in
Table 1.
Table 1: Vibrational Frequencies for Organic Molecules
Bond Type
Specific Context v, cm

Stretching Frequencies
C-H Csp3-H 2800-3000
Csp2-H 3000-3100
Csp-H 3300
C-C C-C 1150-1250
C=C 1600-1670
CC 2100-2260
C-N C-N 1030-1230
C=N 1640-1690
CN 2210-2260
C-O C-O 1020-1275
C=O 1650-1800
C-X C-F 1000-1350
C-Cl 800-850
C-Br 500-680
C-I 200-500
N-H RNH2, R2NH 3400-3500 (two)
, R2NH2
, R3NH
RCONH2, RCONHR' 3400-3500
O-H ROH 3610-3640 (free)
3200-3400 (H-bonded)
RCO2H 2500-3000
N-O RNO2 1350,1560
RONO2 1620-1640, 1270-1285
RN=O 1500-1600
RO-N=O 1610-1680 (two), 750-815
C=N-OH 930-960
S-O R2SO 1040-1060
R2S(=O)O 1310-1350
R-S(=O)2-OR' 1330-1420, 1145-1200
Cumulated systems C=C=C 1950
C=C=O 2150
R2C=N=N 2090-3100
RN=C=O 2250-2275
RN=N=N 2120-2160
Out-of-plane bending vibrations
Alkynes CC-H 600-700
Alkenes RCH=CH2 910, 990
R2C=CH2 890
trans-RCH=CHR 970
cis-RCH=CHR 725, 675
R2C=CHR 790-840
Aromatic mono- 730-770, 690-710 (two)
o- 735-770
m- 750-810, 690-710 (two)
p- 810-840
1,2,3- 760-780, 705-745 (two)
1,3,5- 810-865, 675-730 (two)
1,2,4- 805-825, 870, 885 (two)
1,2,3,4- 800-810
1,2,4,5- 855-870
1,2,3,5 840-850
penta- 870
Carbonyl Stretching Frequencies
Aldehydes RCHO 1725
C=CCHO 1685
ArCHO 1700
Ketones R2C=O 1715
C=C-C=O 1675
Ar-C=O 1690
four-membered cyclic 1780
five-membered cyclic 1745
six-membered cyclic 1715
Carboxylic Acids RCOOH 1760 (monomer)
1710 (dimer
C=C-COOH 1720 (monomer)
1690 (dimer)
1550-1610, 1400 (two)
Esters RCOOR 1735
C=C-COOR 1720
ArCOOR 720
-lactone 1770
o-lactone 1735
Amides RCONH2 1690 (free)
1650 (associated)
RCONHR' 1680 (free)
1655 (associated)
RCONR2' 1650
|-lactam 1745
-lactam 1700
o-lactam 1640
Acid anhydrides 1820, 1760 (two)
Acyl halides 1800

Applications of IR Spectroscopy to Inorganic Molecules
At this time we wish to discuss the applications of IR spectroscopy in inorganic chemistry. It is
true that many so-called inorganic compounds are in reality largely organic, and for these we
look for the same functional group bands in the IR as we do for purely organic compounds.
However, what we wish to consider now are the infrared spectra of relatively simple, purely
inorganic compounds containing only a few atoms--specifically, inorganic salts containing
polyatomic (complex) ions.
Consider a simple inorganic salt, such as KNO2. On the basis of the empirical formula, we might
naively expect there to be a total of 3(4)-6 = 6 normal modes of vibration associated with this
material. However, we know that there is no such thing as a discrete molecule of KNO2, so our
naive calculation leads to incorrect results. In fact, KNO2 consists of an ionic lattice with K+ ions
and NO2- ions arranged in an infinite and very regular array. The crystal consists of essentially
isolated K
ions and NO2
ions. Thus we might expect to be able to consider the vibrational modes
of the cation and anion independently of one another, and it turns out that, at least to a first
approximation, this can indeed be done. In this case, since the potassium ions are monatomic,
they will give rise to no vibrations (3(1)-3 = 0), so we need only consider the nitrite anions. The
VSEPR (Valence Shell Electron Pair Repulsion) Theory leads to the following structure for the
nitrite ion:
It is a bent species, very much like the water molecule in shape. We thus anticipate three normal
vibrational modes for NO2
, corresponding to the diagrams drawn earlier for the H2O molecule,
and they should all be infrared active. In agreement with this expectation, three bands are
observed in the IR spectrum of KNO2: the symmetric stretch at 1335 cm
, the asymmetric stretch
at 1250 cm
, and the bending vibration at 830 cm
(bending vibrations occur in general at lower
frequencies than do stretching vibrations). Moreover, the frequencies of these vibrations are
about the same regardless of counter ion, substantiating the essential independence of the anion
and cation in the crystal. (This independence is only an approximation, but we will not worry
about the complicating factors now.) We can, therefore, diagnose the presence of nitrite ion in a
salt from the infrared spectrum of the material. This diagnostic application can be readily
implemented only when the spectrum of the material is relatively uncomplicated, but despite this
restriction it is an enormously useful application.
Let us turn now to a somewhat more complex case, that of NaNO3. Here we anticipate 3(4)-6 =
6 normal vibrational modes. The infrared spectrum, however, exhibits only three fundamental
bands, at 831, 1405, and 692 cm
. What's happening? First, let's make one thing clear--there is
no doubt that there are 6 normal vibrational modes. The formula is always valid. In the case of
, however, (or for that matter, any similar planar, triangular ion or molecule), the symmetric
stretch, pictured below, is not IR active.

This is because this particular motion does not cause a change in the dipole moment of the ion,
and hence cannot give rise to absorption of IR radiation. This eliminates, then, one of the
anticipated bands from the IR spectrum. Among the remaining 5, there are two sets of doubly
degenerate vibrations--i.e., two instances in which 2 vibrations occur with exactly the same
frequency. Thus although 5 vibrations absorb IR radiation, they are manifested in only three
spectral bands. (The symmetric stretch can be observed in the Raman spectrum--you will learn
about this spectroscopic technique later). However, these absorptions can be used in a diagnostic
sense just as for nitrite.
In similar fashion, other relatively simple anionic (and cationic) species can be identified via
their IR spectra. Spectral data for some of the more common polyatomic ions are given in the
table 2.
Table 2: IR Frequencies of Inorganic Salts
Band Position
Relative Intensity
NaSCN 758 w
940 vw, b
1620 m
2020 s
3330 m
KSCN 746 m
945 vw, vb
1630 m
2020 s
3400 m
NaNO2 831 m,sp
1358 vs
1790 vw
2428 vw
NaNO3 836 m,sp
1358 7.36 vs
1790 vw
2428 vw
Na2SO4 645 w
1110 vs
K2SO4 1110 vs
NaClO3 935 s,sp
KClO3 938 w
962 vs
NaClO4H2O 1100 vs,b
1630 (H2O) s,sp
2030 4 vw
KClO4 627 w
940 vw
1075 s
1140 s,sh
1990 vw
NaBrO3 807 vs
KBrO3 790 vs
NaIO3 767 vs
800 m

We wish now to consider an extension of the concepts already introduced and thereby to further
extend your appreciation of the usefulness of IR spectroscopy for inorganic systems. We have
seen that the IR spectrum of the unperturbed (or "ionic") nitrite anion, NO2
, consists of three
bands at 1335 cm
(vs), 1250 cm
(vas), and 830 cm
(o). This is what we will observe in the IR
spectrum of any inorganic nitrite salt, such as KNO2 or NaNO2, in which the symmetry of the
nitrite anion is unperturbed. It is well known, however, that the nitrite ion can function as a
ligand, and it is conceivable that coordination of NO2
to a metal ion could occur in either of two
ways. These are shown below.

The fundamental question is this: will coordination of NO2
to a metal ion have any effect upon
its infrared spectrum, and, if so, can we predict the effect and use it to diagnose the mode of
coordination? The answer is, yes. The diagrams above show clearly that when NO2
through an oxygen atom, one of the NO bonds is very nearly a double bond, whereas the other is
a single bond. In the free NO2
ion and in structure (b), on the other hand, both NO bonds are
intermediate between single and double bonds. The vibrational frequency of a bond increases as
its strength increases, so we would expect the frequencies of the NO bonds in NO2
to increase in
the order N-single bond-O (in O-bonded) < NO (in N-bonded) < N-double bond-O (in O-
In agreement with this, it has been found that in complexes in which NO2
is bonded through
oxygen, the two N-O stretching frequencies lie in the ranges 1500-1400 cm
for N=O and 1100-
1000 cm
for N-O. In complexes in which NO2
is bonded through nitrogen, the bands occur at
similar frequencies which are intermediate between the ranges above; namely, 1340-1300 cm
and 1430-1360 cm
. Thus it is relatively easy to tell on the basis of IR whether a nitrite ion is
coordinated, and if so, whether it is coordinated through N or O.
As a second example, consider the nitrate ion, which functions as a ligand in (at least) the
following ways:

These diagrams show clearly that, regardless of which of the three types of coordination occurs,
the three oxygen atoms, which are identical in the free nitrate ion, are no longer identical in the
coordinated NO3
ion. In all three cases, two of the oxygens are equivalent and the third is unique.
We say that coordination has "reduced the symmetry" of the nitrate ion. The net effect here is to
change what was originally an AB3 type species to an AB2C type.

Since C is different from B, chances are that the molecule now has a dipole moment. More
importantly, the symmetric stretch will now most likely cause a change in dipole moment, and
will therefore become IR active.
Similarly, whereas in AB3 the asymmetric stretch is doubly degenerate (i.e., two independent
vibrational modes exist but occur at the same frequency), in AB2C there will be two asymmetric
stretches of different energy.
Thus the single band in the IR spectrum of free NO3
due to the asymmetric stretch will become
two bands when NO3
becomes coordinated by any of the modes pictured earlier. Similar
considerations hold for the degenerate bending vibration. We therefore expect to see 6 IR bands
for coordinated NO3
and it is very easy indeed to distinguish coordinated from free (that is, ionic)
nitrate. It is generally true that the more symmetrical a molecule or ion is, the fewer the number
of bands that will appear in the IR spectrum. This is nicely illustrated by the nitrate ion.

Magnetism in Transition Metal Complexes
Magnetism in Transition Metal Complexes
When a piece of matter is placed in a magnetic field, H (italic signifies a vector quantity), the
matter becomes magnetically polarized; that is, a magnetic field is set up in the matter as a result
of its presence within the external field, and it has been found experimentally that the strength of
the internal field is proportional to the strength of the applied (external) field. We express this
mathematically by equation (1) where M is the magnetic polarization of the matter and _ is a

M = _H (1)

proportionality constant called the volume magnetic susceptibility. It has been further
demonstrated by experiment that _ may be either negative or positive. Materials for which _ is
small and less than 0 are called diamagnetic materials. Such behavior is always found for
materials that contain no unpaired electrons. Most (but not all) organic compounds qualify as
diamagnetic materials, since all their electrons are paired. Diamagnetic behavior is due to small
fields induced in the sample by the applied field that are absent if no external field is present. All
materials, regardless of any additional magnetic behavior they may display, exhibit
diamagnetism. Materials for which _ is greater than 0 are found to contain one or more unpaired
electrons. If 0 < _ <1 (the usual situation), the material is said to be paramagnetic. If on the other
hand _ > 1, the material is termed ferromagnetic. Notice that _ being greater than 1 means that
the magnetic field set up in the sample of matter is greater in magnitude than the applied field!
This behavior is exhibited by metallic iron (hence the word ferromagnetic), nickel, and some
other metals. Ferromagnetism, however interesting, will not concern us any more at present.
We are interested now in the phenomenon of paramagnetism, which arises whenever a molecule
contains unpaired electrons. Oxygen is paramagnetic because it contains two unpaired electrons.
NO2 is paramagnetic since it contains an odd number of electrons. (Any substance containing an
odd number of electrons must be paramagnetic. Nature usually avoids this situation in
compounds of the representative elements, but makes up for it in transition and inner transition
elements, where there can be as many as 7 unpaired electrons per molecule.) Organic free
radicals are paramagnetic due to the presence of an odd electron (remember the methyl radical,
CH3 , in free radical halogenation?). As it happens, complexes of most transition metals are
paramagnetic as a result of the presence of unpaired electrons in the split d orbitals. We have
already encountered an example of this in the complex Cr(NH3)6
, which contains 3 unpaired
electrons. Consider another example, this time involving Fe
, whose electronic configuration is
in the absence of ligands. We would expect the free gaseous ion to contain 5 unpaired
electrons, as indeed it does--the electrons are distributed in the five degenerate d orbitals,
according to the Pauli Exclusion Principle and Hund's Rules, as shown below:

Hund's Rules state that electrons filling a set of degenerate orbitals will fill them so as to
maintain their spins parallel for as long as possible. Similarly, the complex Fe(H2O)6
, present in
strongly acid aqueous solution, contains 5 unpaired electrons. However, the very stable complex
, named hexacyanoferrate(-3), contains only one unpaired electron, even though it also
contains Fe(III). We deduce from this that the nature of the ligands must in some way influence
the pairing of electrons. But how? Let's call on what we have learned about the splitting of the d
orbitals by the ligands. Figure 2 shows the situation in terms of an energy level diagram.

In the complex, 5 electrons must distribute themselves among the d orbitals, which as a result of
the presence of 6 ligands are no longer all degenerate. There is no ambiguity about where the
first three electrons will go--one electron will enter each of the three degenerate orbitals in the n
set. The fourth electron, however, is faced with a choice: it can either pair up with one of the
electrons in a lower orbital, requiring the expenditure of an amount of energy, P, called the
pairing energy; or it can occupy one of the orbitals in the upper doubly degenerate set at the
expense of the energy, Ao , since the upper set, o*, is less stable by than the lower set, n. The
electron will take the option which requires the expenditure of the least energy. If Ao < P, it will
occupy one of the o* orbitals. If Ao > P, the electron will pair up in n. The fifth electron will be
faced with the same choice, and will make the same decision. Two situations are therefore
possible in octahedral complexes of Fe

In one case, five unpaired electrons are present. This is called the high spin (HS) case and must
correspond to the situation in Fe(H2O)6
. In the second case, called the low spin (LS) case, only
one unpaired electron is present--the maximum possible amount of electron pairing has occurred.
This is the situation which in Fe(CN)6
. We conclude, then, that when H2O is the ligand, Ao < P
and that when CN- is the ligand, Ao > P (P remains essentially the same for a given metal ion,
regardless of ligand, and can be obtained from spectroscopic measurements of the free metal ion,
in this case Fe
.) We call water a relatively "weak-field ligand" and cyanide a "strong-field
Any ion having as few as 4 or as many as 7 d electrons can exhibit either high- or low-spin
behavior in an octahedral complex. You should work out the numbers of unpaired electrons
expected in octahedral complexes of metal ions with configurations d1 to d9 to convince yourself
of this. The theory that we have developed above explains beautifully most aspects of the
magnetic behavior of transition metal complexes, the exceptions being the more subtle aspects
that we will avoid for the time being. Let's turn now to the relationship between the number of
unpaired electrons possessed by a molecule and its behavior in a magnetic field.
There are two sources of magnetic behavior in matter: 1) orbital motion of electrons; 2) spin of
electrons. We will deal with spin motion only now, since it is the most important source of
magnetic behavior in complexes of transition metals. Pictured below is an electron spinning
(rotating) about its own axis.

This motion is analogous to the rotation of the earth about its axis. Since the electron is a charged
particle, this rotational motion constitutes an electric current. To see this more clearly, mentally
replace the electron with a loop of wire in which a current is flowing:

Recall from your study of electricity and magnetism in physics, that a flow of current always
generates a magnetic field. When the current is flowing in a loop, the direction of the magnetic
field is perpendicular to the plane of the loop. Thus

The spin of the electron about its axis, since it is an electric current, similarly generates a
magnetic field parallel to the axis of rotation. This magnetic field is called the spin magnetic
moment of the electron, and is given the symbol S. The arrow over the symbol indicates that the
magnetic moment is a vector quantity. Now rotational motion of any kind always generates
angular momentum, which is also a vector parallel to the axis of rotation. The magnetic moment
and the angular momentum are therefore colinear vectors. Furthermore, their magnitudes are
directly proportional. This is indicated in the following equation
= L (2)
where L = angular momentum and is the proportionality constant relating magnetic moment
and angular momentum. When a paramagnetic sample is placed in an external magnetic field, the
individual spin magnetic moments of the unpaired electrons all line up with the field, just as iron
filings line up along the magnetic lines of flux generated by a bar magnet. Their vector sum is
the magnetic polarization defined by equation (1). Thus we see that magnetic polarization, which
is a macroscopic property, is related to individual spin magnetic moments, which are
microscopic properties of the system.
It can be shown that the magnetic moment of an individual ion in a sample is related to the
number of unpaired electrons on the ion by the following equation.
S = [n(n + 2)]
Bohr magnetons (3)
The Bohr magneton is a convenient unit for expressing magnetic moments, and is defined in
terms of fundamental constants as 1 BM = eh/4tmc. Here e = the charge on the electron, h =
Planck's constant, m = the mass of the electron, and c = the speed of light, and, in equation (3), n
= the number of unpaired electrons per ion. We can therefore calculate the number of unpaired
electrons per molecule of sample if we can measure the magnetic moment. In practice, we can
relatively easily measure the molar magnetic susceptibility of a material, which is then related to
the magnetic moment by equation (4).
S = 2.84(_MT)

1. F.A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, 4th edition, John Wiley and
Sons, New York, 1980.

Nuclear Magnetic Resonance Spectroscopy (NMR)
Nuclear Magnetic Resonance Spectroscopy

The nuclei of some atoms, but not all, behave as if they were rotating, or spinning, about an axis
passed through them, much as a top spins about its central axis. This is quite easily visualized in
terms of the particle nature of the nucleus; it is less easily visualized in terms of the wave picture,
which by now we know is another face of nature that is manifested in the atomic/molecular
realm. Spin of nuclei is similar to electron spin. Examples of atoms whose nuclei spin are
hydrogen, fluorine, the 13 isotope of carbon, and the 15 isotope of nitrogen. There are many
others that will not be listed here. The focus in this chapter will be on the spin of the hydrogen
nucleus, because hydrogen atoms occur very frequently in molecules and are therefore very
useful in determination of structure. When placed in a strong magnetic field, the spinning motion
of the hydrogen atom gives rise to two energy levels. These are shown in an energy level
diagram in Figure 1.
The spin can be promoted from the lower to the higher level by interacting with and absorbing
energy from electromagnetic radiation in the radio frequency (RF) region of the spectrum. A
typical radio photon has a frequency of 10
, a wavelength of 300 meters (about the length of
three football fields), and an energy of 6.6 x 10
Joules. The separation between the two spin
energy levels is a sensitive function of the molecular environment of the hydrogen atom in a
molecule. Thus hydrogen atoms in different environments absorb photons of different energies.
By plotting the amount of energy absorbed by the spinning nuclei versus the frequency of the RF
radiation applied to the molecule, we obtain the nuclear magnetic resonance (NMR) spectrum of
the molecule. This spectrum provides information about the chemical environment of the
spinning hydrogen nucleus, and can be used to deduce the atomic bonding patterns in the
molecule. NMR has now been developed to such a level of sophistication that it can be used to
determine the 3-dimensional structures of huge protein molecules in solution. Recently, nuclear
magnetic resonance spectroscopy has found medical applications, in which context it is known
as magnetic re sonance imaging (MRI). MRI utilizes the spinning motions of atomic nuclei to
provide a map of the internal structure of human body tissue.
We will now discuss the nature of NMR spectra in a systematic way, beginning with spectra of
simple molecules, and gradually escalating in complexity. As we proceed through the discussion,
we will gradually introduce some of the jargon used by practicing chemists when discussing
NMR. As a first bit of jargon, we will henceforth refer to hydrogen atoms as protons. This is
appropriate, because it is the nucleus of the hydrogen atom that is spinning, and this nucleus
indeed consists of a single proton. We begin by considering the NMR spectrum resulting from
the molecule shown in Figure 2a.

figure 2a
The molecule has a single proton on the right (on carbon 1), and a pair of protons on the left (on
carbon 3). Carbon atoms 1 and 3 are separated by a carbon atom attached to two chlorine atoms.
The single proton on the right is attached to a carbon atom that is in turn attached to 2 chlorine
atoms. In contrast, each proton on the left is attached to a carbon atom that is in turn attached to
one chlorine atom, and a second hydrogen atom. The environments of the protons on carbon 1
and carbon 3 are clearly different. The energy level spacing of the two types of protons should
thus be different, and two signals, one for each type of proton, should appear in the NMR
spectrum. The spectrum is shown in Figure 3a (below).

figure 3a
Several aspects of this spectrum are important. First, the single sharp signal at exactly 0 ppm is
not due to the subject molecule, but is instead due to a reference compound named
tetramethylsilane, or TMS. The structure of TMS is shown in Figure 2d.

figure 2d
By general agreement, the positions of NMR signals are always reported relative to the position
of the signal for TMS. Second, the unit used to measure resonance position, ppm (parts per
million), is not a unit of energy. It has no units at all. It may be regarded as a measure of the shift
in position between the TMS resonance and a particular resonance in the compound of interest. It
is usually called the chemical shift. The chemical shift gives an indication of the chemical
environment in which the spinning nucleus is found, as we will see shortly. Ignoring the TMS
signal, then, which we can expect to be present in all NMR spectra, we see that there are indeed
two signals. Interestingly, the sizes, or intensities, of the signals are different. The right signal
appears to be twice as tall as the one on the left. This suggests that the right signal is due to the
pair of protons on carbon 3, and the left signal to the single proton on carbon 1. It also appears
that there is a relationship between the position of a signal in the spectrum, and the number of
chlorine atoms in the immediate environment of the proton(s) giving rise to the signal. We
summarize our observations of the simple spectrum in Figure 3a in terms of three rules:
Rule 1: Each unique proton environment generates one signal.
Rule 2: The intensity (size) of an NMR signal gives a measure of the number of
equivalent atoms responsible for the signal. A two-proton signal is twice as large
as a one-proton signal.
Rule 3: The greater the number of electronegative atoms near a proton, the further
to the left of TMS the proton signal will be.
Rule 3 requires some comment. In Figure 3a, the signal due to the hydrogen atom on carbon 1 is
shifted further away from TMS than is the signal of the hydrogens on carbon 3. In NMR jargon,
the left signal is said to befurther downfield (meaning further to the left) than the right signal.
The reason for this is that the carbon-1 proton is close to two electronegative chlorine atoms.
These pull electrons away from carbon 1, which in turn pulls them away from the hydrogen atom.
The less electron density a hydrogen atom has around it, the further downfield its NMR
resonance occurs. This type of consideration helps us to assign signals to particular hydrogen
atoms in molecules.
Figure 2b shows a molecule that appears simpler than the molecule in Figure 2a, but is in fact
somewhat more complex in NMR terms.

figure 2b
The molecule in Figure 2b can be obtained from that in Figure 2a by removing the central
carbon atom, bringing the proton bearing carbons together. Clearly the carbon 1 proton is still in
a different environment than are the pair of carbon 2 protons, so we might expect the NMR
spectrum of this new molecule to be very simil ar to that of the three-carbon molecule.
Specifically, we might expect two signals, one twice as intense as the other, with the less intense
one downfield. The spectrum is shown in Figure 3b. Although there are two signals, in roughly
the expected locations, the signals appear to be split into subsignals. The upfield signal now
consists of two, and the downfield signal of three, closely-spaced subsignals. Chemists call the
upfield signal a doublet, and the downfield signal a triplet, to indicate the number of subsignals.
Apparently, there is a complication showing up here that is not present in the spectrum in Figure
3a. As we will see, this complication is what makes NMR so useful for determination of
structure. The splitt ing of signals seen in Figure 3b occurs because protons on neighboring
atoms "feel" each others spins. A spinning nucleus is, in fact, a tiny magnet. When it is close
enough to another proton, the second proton feels the small magnetic field of its neighbor as a
tiny perturbation on the large magnetic field applied to the sample. The effect of this proton-
proton interaction is to cause small changes in the energy level spacings of the proton that show
up as the splittings that we see in Figure 3b. Interestingly, the number of subsignals into which a
signal is split appears to be one greater than the number of neighboring protons.

figure 3b
We can now add a couple of new rules to our list:
Rule 4: Protons on neighboring atoms interact with each other, and split each
others signals.
Rule 5: The number of subsignals in a multiplet is one more than the number of
neighbor protons.
Clearly the splitting of signals due to neighboring atoms (called spin-spin splitting in the jargon
of the chemist) is of potentially great value in assigning signals and in determining structure; it
tells us the number of protons on the atom next door to the atom bearing the protons being
To test our rules, we consider the molecule in Figure 2c.

figure 2c
Again we see only two different proton environments here. The two carbon-1 protons are in one
environment; the three carbon-2 protons are in a different environment. We expect two signals,
one of total intensity two and the other of total intensity three. The signal of intensity two should
be further downfield because the carbon 1 protons have an electronegative bromine atom in their
neighborhood. We expect the downfield signal to be split to a quartet due to interaction with the
three protons on carbon 2; and the upfield signal to be split to a triplet via interaction with the
two protons on carbon 1. The spectrum is in Figure 3c, and appears much as we expected it to.
The NMR rules seem to work fine.

figure 3c
We consider one final example, which will reveal a couple of other useful subtleties of NMR
spectra. The molecule of interest and its NMR spectrum are shown in Figure 4.

figure 4
The protons labelled "a" in the figure experience the same environment (this is clear from a
model of the molecule), and are expected to give one signal. This signal should be the furthest
upfield because these protons are furthest removed from the electonegative oxygen atom.
Because there is a single proton, "b", on the neighboring carbon atom, the signal for protons "a"
should be a doublet with total relative intensity 6. This is clearly seen in the spectrum. Proton "c"
should give the furthest downfield signal because it is attached to an oxygen-bearing carb on
atom. This, too, is expected to be a doublet due to interaction with proton "b". Although the
splitting of the proton "c" signal is small, it is discernible in Figure 4. Note that the signal from
"c" is very far downfield, much more so than th e signals influenced by chlorine atoms in
previous examples. This results from the very high electronegativity of the oxygen atom, which
substantially depletes the attached carbon atom of electron density. Finally, we examine the
signal for proton "b". This is our first encounter with a proton that interacts with two other sets of
protons, and it is important to understand how the splitting works in a situation like this. The
signal shows a total of 14 lines, which is many more than we have encountered in a multiplet up
to this point. The explanation for all of these lines runs as follows. First, the signal for "b" is split
to 7 lines by the interaction with the 6 "a"-type protons on neighboring carbon atoms. Then, each
component of the 7-line pattern is split to two lines by the interaction with proton "c". The total
is 14 lines. In terms of this interpretation, Figure 4 clearly shows a 7-line pattern, each
component of which is split into two lines. This pattern is called a doublet of septets, to indicate
that it results from interaction of "b" with two distinctly different types of protons. On the basis
of the isobuthylaldehyde example, we are in a position to state two additional rules.
Rule 6: A proton on an oxygen-bearing carbon is shifted very far downfield.
Rule 7: A proton with n neighboring protons on one side and m on the other will
give a signal split into (n+1)(m+1) components.
The Greek letter, o, symbolizes the chemical shift in units of parts per million. This brief
description is sufficient to allow us to visualize and, if desired, even draw the spectrum, and to
interpret it in terms of structure.
In this section, we have considered a number of NMR spectra and from them have developed a
simple set of rules for their interpretation and prediction. It is important to realize that, although
these rules are very useful in understanding the NMR spectra of relatively simple molecules, the
spectra of many molecules involve complexities that our simple rules are unable to handle.
Nonetheless, we have laid the groundwork for an understanding of NMR spectra that can be
expanded on in more advanced books.
Table 4-1 gives chemical shifts characteristic of a variety of proton environments.
Table 4-1: NMR Proton Chemical Shifts
Type of Proton Downfield Shift from TMS

RCH3 0.8-1.0
RCH2R 1.2-1.4
R3CH 1.4-1.7
R2C=C(R)-CH3 1.6-1.9
ArCH3 (Ar stands for a benzene ring) 2.2-2.5
RCH2Cl 3.6-3.8
RCH2Br 3.4-3.6
RCH2I 3.1-3.3
ROCH2R 3.3-3.9
RCH2OH 3.3-4.0
RC(=O)CH3 2.1-2.6
RC(=O)H 9.5-9.6
R2C=CH2 4.6-5.0
R2C=C(R)H 5.2-5.7
ArH 6.0-9.5
RCCH 2.5-3.1
ROH 0.5-6.0
RC(=O)OH 10-13
ArOH 4.5-7.7
R-NH2 1.0-5.0