T. G.

Dunne
Reed
Spectra of Cr(lll) Complexes
College
Portland, Oregon 97202
An inorganic chemistry experiment

Crystal field theory (1, 2) predicts for the d1 and d9 is that the e set of orbitals is lower
transition metal octahedral complexes that the d in energy than the t set in the case of d9, since this
orbitals are split in the manner shown in Figure 1. system is equivalent to one electron hole or effective
The original assumption of this theory that the d elec- positron interacting with the ligands (2). Since the
trons have a coulombic interaction with the ligands con- charge of the interacting particle is reversed, the
sidered as point charges is certainly not correct, and a energy levels resulting from the interaction must also
priori calculations of the crystal field splitting parameter, be reversed compared to d1.
10 Dq, based on this model are generally in poor agree- The spectra of transition metal complexes where the
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ment with experimental values obtained from visible metal ion has a configuration dn, where 1 < n < 9,
spectra (3). However, because of the octahedral sym- is complicated by additional levels arising from inter-
metry it is true that the splitting of the d levels pre- actions between the d electrons. Thus it would seem
dicted by crystal field theory is qualitatively correct. that the simplest experimental illustration of the
That is, whatever the nature of the ligand-metal inter- spectrochemical series would be the spectroscopic
action, the dxl, dVz, and dxv orbitals will form a three- 2
d3j)
Eg (d
fold equivalent set (t set) and the dxt- and orbitals
will form a two-fold equivalent (e set) in the complex.* 1

Thus, 10 Dq, the energy difference between these two

sets, may be determined by experiment, even though
'29

its accurate theroretical calculation is difficult.

It is found that spectroscopically measured values
of 10 Dq fall in a sequence of increasing energy which N-aTg(dxy, dX2, dyz)
*29

is quite independent of the metal ion. That is, al- Figure 2. Energy splitting of
Figure 1. Energy splitting of the 2D
though the value of 10 Dq for a given ligand is different free ion level for on ion with the dl con-
the 4F free ion level of the d3
configuration in an octa-
for each metal ion, the qualitative sequence of increas- figuration in the octahedral crystal field. hedral crystal field.
ing energy on ligand substitution is essentially the
same and therefore independent of the metal ion. investigation of octahedral or tetrahedral complexes of
This sequence, the so-called spectrochemical series d1 or d9 ions. There are problems in both cases, how-
(1,2), runs as follows: ever. The octahedral complexes of Ti(III), which
I -

< Br- < Cl- < F- < C2H3OH < II20 < Nils <
represent the best d1 possibility, are quite sensitive to
air oxidation and a study of their spectra would
Ethylenediamine <N02~ < CN~ necessarily involve inert atmosphere techniques for
It should be emphasized that, although crystal field preparation and handling. The Ti(III) case may be
theory would suggest some such sequence, the spectro- left as an exacting laboratory exercise for the more
chemical series is empirically determined. advanced and experimentally adept student.
The interpretation of spectra in terms of the spectro- The complexes of Cu(II) are experimentally feasible
chemical series is in principle most easily done in the d9 representatives, but, while they are easy to prepare
case of octahedral or tetrahedral2 complexes of metal and handle, they generally deviate significantly from
ions with d1 or d9 configurations. In these cases there either octahedral or tetrahedral symmetry.
is no interaction with other d electrons and since the A good compromise between experimental simplicity
d orbitals interact uniformly with the core of non- and easy spectroscopic analysis exists in the case of
valence metal electrons the only d level splitting is Cr(III) complexes since crystal field theory predicts
due to the interaction of the d orbital with the ligands. (4) that the 4F Russell-Saunders ground state of the
Thus, a single spectral transition of energy, 10 Dq, is free chromium ion is split into three levels of symmetry
predicted. The only qualitative difference between designation, 4A2g, 4T2g, and 4Tig, as shown in Figure 2,
where the energy separation between the two lower
levels, 4A2g, and 4T2g, is 10 Dq. Thus, in the Cr(III)
case although we expect to find a more complicated
We thank the American Cyanamid Corp. and the National
Science Foundation for the financial aid in the purchase of the spectrum than in the case of d1 and d9 complexes, the
Beckman DB Spectrophotometer. energy of the longest wave length peak should give
In the usual case where there is significant covalent bonding
1 us a good approximation to the crystal field parameter,
between the metal ion and the ligands we expect that these orbi- 10 Dq.
tals will be better represented by linear combinations of the metal
d orbitals and appropriate ligand orbitals. The Experiment
2
The d orbitals in a tetrahedral crystal field are split in the
same manner as the octahedral case, except that the e set is at The purpose of the experiment is three-fold. First,
lower energy than the t set. the student verifies that the spectrochemical series

Volume 44, Number 2, February 1967 / 101

holds in the ease of Cr(III) complexes by determination of trace amounts of a substitutionally labile Cr(II)
of the spectra of Cr(H20)e(N03)3-3H20,3 and triethyl- species is probably involved.
enediaminechroiniuru(III) chloride,'Cr{en)3Ch. (Where,
although the symmetry of the molecule is not octa- Tris(%,4-pentanedionato)chromium (III). The method
of preparation is that given in the literature (6).
hedral, the nitrogen atoms are arranged in an octa-
hedral array about the chromium ion.4) Secondly, To 100 ml H,0 are added 2.66 g of CTC'1S-6H20 (0.01 mole)
the student is asked to fit a new ligand into the speetro- and, after complete solution, 20 g of urea and 6 g of acetylace-
chemical series by preparing another complex and tone (0.06 mole). The reaction mixture is covered with a
watch glass and heated on a steam bath overnight. As the
measuring its spectrum. We have chosen tris(2,4- urea hydrolyzes to release ammonia, purple crystals of the
pentanedionatof Chromium (III) for this purpose. Fi- complex form. Recrystallize the crude product by dissolving
nally, the student determines the spectra of CrCl3- in a minimum quantity of benzene, filtering, and adding hex-
6H20 (green colored reagent grade material) just after ane or heptane to precipitate the Cr(CsH702)a.

preparation of the solution and at later times over a CrCh 61120. The reagent grade salt consists pri-
period of about 8 hours. He is then asked to explain marily of the green form of this compound which
the time dependence of the spectra by information is known to have the structural formula (7) trans-
previously obtained. [Cr(H20)4Cln]CT2Hn0. This was used without fur-
ther purification.
The spectra shown in Figures 3 and 4 were deter-
mined on a Beckman DB Spectrophotometer equipped
with a strip chart recorder. The extinction coefficients
were calculated by the formula

t
log h/I
cl

The cell length, l 1 cm

= and the molar concentration
c, of each complex was adjusted to give a transmittance,
I/In = 0.5 at the long wavelength absorption maxima.
From Figure 3 it is seen that Cr(en)33+ has a transi-
tion at lower wavelengths than that for Cr(H2OV+,
which is the result predicted from the spectrochemical
series. The positions of the long wavelength absorp-
tion peak (10 Dq) for each of the complexes is given
in the table in cm-1, a unit which is proportional to
the energy of the transition.
Figure 3. The absorption spectrum of Cr(en)3Cl3 *3.5 H20 in water (solid
line), the spectrum of CrlFhOkfNOghOFbO in wafer (dotted line), and the
There are two noteworthy points concerning the
spectrum of Cr(C6H202h in benzene (broken line). spectra shown in Figure 3. First, the spectrum of

Preparation of Compounds
Triethylenediaminechromium{III)Chloride. The meth-
od of preparation of the complex in its hydrated
form is essentially that of Bailar and Work (5) and
proceeds as follows:
To 6.7 g OCI3-6H2O, which has been thoroughly ground in
a mortar and pestle, add 0.8 g decolorizing charcoal (catalyst)
and 9.5 g ethylenediamine. Heat mixture in an open beaker
on a steam bath overnight. After cooling, cover with 25 ml
ethanol and, after an hour, grind mixture in a mortar, filter off
alcohol, and repeat, several times with smaller portions of
ethanol to remove all excess ethylenediamine (one need not
wait an hour in these steps). After drying, stir mixture with
25 ml of 1.7 N HC1 at 60° for one minute, filter rapidly with a
Buchner filter, and add the filtrate immediately to an ice-cooled
Figure 4. The solid line represents absorption spectrum of an aqueous
mixture of 40 ml ethanol and 25 ml cone. HC1, the ethanol-HCl solution of CrCl3*6H20 immediately after preparation; the short dashes
mixture being contained in a beaker. The orange Cr(en)3CI3- represent the same solution after two hours; the dot-dash line represents
3.5 H20 which separates is filtered out, washed with ethanol, the solution after 6.5 hours; and the long dashes represent the spectrum
and air dried. of CrfHiOjglNOata»3H20.

The catalytic mechanism for this reaction is still

somewhat of an open question, although the formation tris(2,4-pentanedionato)chromium(III) appears to
have only one absorption maximum with steeply rising
1
Reagent grade salt used with further purification. absorption in the region of the expected second maxi-
4
This experiment may be easily expanded to include the prepa- mum. The reason that the second crystal field transi-
ration and spectroscopic study of complexes of other ligands. tion is not readily detected is that it is obscured by the
For instance, the student might prepare a compound containing intense absorption of light associated with electronic
the ion Cr(NH3)63 + in order to verify that the spectrum of this
transitions between orbitals that are primarily ligand-
Compound is very similar to that of Cr(en)3Cls, as would be ex-
pected if the atoms directly bonded to the metal ion play a pri- like in nature and orbitals that are primarily metal-
mary role in determining the splitting of the d levels. like in nature. Such transitions are called charge

102 / Journal of Chemical Education

transfer transitions and commonly are associated with octahedral complexes in Figure 3. This is in agree-
much stronger absorption of light than are crystal field ment with what is usually found for such complexes
transitions. provided that the two different types of ligands are not
Secondly, the absorption maxima for Cr(H20)6*+ too widely separated in the spectrochemical series. In
are relatively small compared to those for Cr(en)3s+ these pseudo octahedral cases 10 Dq is found to be
and Cr(C&H702)3. This is qualitatively explained by intermediate between that expected for a complex
the lower symmetry of the ligand arrangement around containing ligands entirely of one type and that ex-
the metal in the case of the chelate complexes. Spe- pected for a complex containing entirely the other
cifically the chelates lack a center of symmetry whereas type of ligand. In the present case the lower value
the hexahydrate ion has a center of symmetry. Since of 10 Dq for Cr(H20)4CI2+ compared to that for
the hypothetical static cent rosy mmetrie ligand arrange- Cr(H20)e3+ is in agreement with the lower position of
ment should result in the crystal field transitions being Cl in the spectrochemical series.
-

completely forbidden for the absorption of light by From Figure 4 we also see that the spectrum over a
the electric dipole mechanism (8), we might anticipate period of several hours transforms to one rather similar
that a complex which is centrosymmetrie would show to that of the Cr(H20)e3+ indicating that a rather slow
weaker transitions even though vibrations always cause aquation reaction has gone almost to completion.
small instantaneous distortions from the centrosym- The work of Gates and King (9) indicates that for longer
metric arrangement. periods of time the CrCl3 6H20 spectra should approach
that of Cr(H20)e3 + quite closely. This was indeed
Experimental Values of 10 Dq of Cr(III) Complexes found to be the case by students who let their solutions
stand for several days before measuring the final
Compound 10 Dq (cm"1)
spectrum.
[Cr(H.O)4CyCl-2IUO 15,400“
[Cr(H20)a](N03)s-3H<0 17,100 Literature Cited
CrfCJLOds 17,750
Cr( en )3C13 3.5H20
•
21,300 (1) to Transition Metal Ion
Orgel, L. E., “An Introduction
This is an approximate value since the solid was probably
* Chemistry: Ligand Field Theory,” John Wiley & Sons,
not entirely the dichioro complex, and as is seen in Figure 4 the Inc., New York, I960.
spectrum changes with time, so although the spectrum was run (2) Cotton, F. A. and Wilkinson, G., “Advanced Inorganic
as soon as possible after solution preparation there was probably Chemistry'; A Comprehensive Text,” Interscience Pub-
a small error due to this. lishers (division of John Wiley & Sons, Inc.), New York,
1962.
From the table it is obvious that the 2,4-pentane- (3) Cotton, F. A., J. Chem. Editc., 41, 466 (1964).
dionato complex lies slightly above water in the (4) Ballhausen, C. J., “Ligand Field Theory,” McGraw-Hill
Book Co., New York (1962), p. 235.
spectrochemical series, so tentatively the 2,4-pentane- (5) Bailar, J. C. and Work, J. B., J. Am. Chem. Soc., 67, 176
dionato ion may be placed between H20 and NH3 (1945).
in this series, since we anticipate that NH;; will be (6) Moeller, T., (Editor), “Inorganic Syntheses,” Vol. V,
close to ethylenediamine. McGraw-Hill Book Co., New York, 1957, p. 130.
(7) Dance, I. G. and Freeman, H. C., Inorg. Chem., 4, 1555
Figure 4 shows the time variation of the spectrum (1965).
of CrCls 6FFO. The spectra of CrCl3 GH20 illustrate (8) Dunn, T. M., “The Visible and Ultra-violet Spectra of Com-
a point of rather general application in interpreting plex Compounds,” in “Modem Coordination Chemistry,”
crystal field spectra. This is, that even though the (Editors: Lewis, J. and Wilkins, R. G.) Interscience
Publishers (division of John Wiley & Sons, Inc.), New
chromium is initially surrounded by four water mole-
York, 1960, p. 280.
cules and two chloride ions, the spectra of the freshly (9) Gates, II. S. and King, E. W., J. Am. Chem. Soc., 80, 5011
prepared solution are very similar to the more nearly (1958).

Volume 44, Number 2, February 1967 / 103