T. G.
Dunne
Reed
Spectra of Cr(lll) Complexes
College
Portland, Oregon 97202
An inorganic chemistry experiment
Crystal field theory (1, 2) predicts for
transition metal octahedral complexes that the d
orbitals are split in the manner shown in Figure 1.
The original assumption of this theory that the d elec-
trons have a coulombic interaction with the ligands con-
sidered as point charges is certainly not correct, and a
priori calculations of the crystal field splitting parameter,
10 Dq, based on this model are generally in poor agree-
Downloaded via CALIFORNIA STATE UNIV LONG BEACH on February 19, 2020 at 21:48:05 (UTC).
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
ment with experimental values obtained from visible
spectra (3). However, because of the octahedral sym-
metry it is true that the splitting of the d levels pre-
dicted by crystal field theory is qualitatively correct.
That is, whatever the nature of the ligand-metal inter-
action, the dxl, dVz, and dxv orbitals will form a three-
fold equivalent set (t set) and the dxt- and orbitals
will form a two-fold equivalent (e set) in the complex.*
Thus, 10 Dq, the energy difference between these two
sets, may be determined by experiment, even though
its accurate theroretical calculation is difficult.
It is found that spectroscopically measured values
of 10 Dq fall in a sequence of increasing energy which
is quite independent of the metal ion. That is, al-
though the value of 10 Dq for a given ligand is different
for each metal ion, the qualitative sequence of increas-
ing energy on ligand substitution is essentially the
same and therefore independent of the metal ion.
This sequence, the so-called spectrochemical series
(1,2), runs as follows:
I -
< Br- < Cl- < F- < C2H3OH < II20 < Nils <
Ethylenediamine <N02~ < CN~
It should be emphasized that, although crystal field
theory would suggest some such sequence, the spectro-
chemical series is empirically determined.
The interpretation of spectra in terms of the spectro-
chemical series is in principle most easily done in the
case of octahedral or tetrahedral2 complexes of metal
ions with d1 or d9 configurations. In these cases there
is no interaction with other d electrons and since the
d orbitals interact uniformly with the core of non-
valence metal electrons the only d level splitting is
due to the interaction of the d orbital with the ligands.
Thus, a single spectral transition of energy, 10 Dq, is
predicted. The only qualitative difference between
We thank the American Cyanamid Corp. and the National
Science Foundation for the financial aid in the purchase of the
Beckman DB Spectrophotometer.
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-
tals will be better represented by linear combinations of the metal
d orbitals and appropriate ligand orbitals.
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
lower energy than the t set.
the d1 and d9 is that the e set of orbitals is lower
in energy than the t set in the case of d9, since this
system is equivalent to one electron hole or effective
positron interacting with the ligands (2). Since the
charge of the interacting particle is reversed, the
energy levels resulting from the interaction must also
be reversed compared to d1.
The spectra of transition metal complexes where the
metal ion has a configuration dn, where 1 < n < 9,
is complicated by additional levels arising from inter-
actions between the d electrons. Thus it would seem
that the simplest experimental illustration of the
spectrochemical series would be the spectroscopic
2
d3j)
Eg (d
1
'29
N-aTg(dxy, dX2, dyz)
*29
Figure 2. Energy splitting of
Figure 1. Energy splitting of the 2D
free ion level for on ion with the dl con-
the 4F free ion level of the d3
configuration in an octa-
figuration in the octahedral crystal field. hedral crystal field.
investigation of octahedral or tetrahedral complexes of
d1 or d9 ions. There are problems in both cases, how-
ever. The octahedral complexes of Ti(III), which
represent the best d1 possibility, are quite sensitive to
air oxidation and a study of their spectra would
necessarily involve inert atmosphere techniques for
preparation and handling. The Ti(III) case may be
left as an exacting laboratory exercise for the more
advanced and experimentally adept student.
The complexes of Cu(II) are experimentally feasible
d9 representatives, but, while they are easy to prepare
and handle, they generally deviate significantly from
either octahedral or tetrahedral symmetry.
A good compromise between experimental simplicity
and easy spectroscopic analysis exists in the case of
Cr(III) complexes since crystal field theory predicts
(4) that the 4F Russell-Saunders ground state of the
free chromium ion is split into three levels of symmetry
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
spectrum than in the case of d1 and d9 complexes, the
energy of the longest wave length peak should give
10 Dq.
The Experiment
The purpose of the experiment is three-fold. First,
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 the spectra of Cr(H20)e(N03)3-3H20,3 and triethyl-
enediaminechroiniuru(III) chloride,'Cr{en)3Ch. (Where,
although the symmetry of the molecule is not octa-
hedral, the nitrogen atoms are arranged in an octa-
hedral array about the chromium ion.4) Secondly,
the student is asked to fit a new ligand into the speetro-
chemical series by preparing another complex and
measuring its spectrum. We have chosen tris(2,4-
pentanedionatof Chromium (III) for this purpose. Fi-
nally, the student determines the spectra of CrCl3-
6H20 (green colored reagent grade material) just after
preparation of the solution and at later times over a
period of about 8 hours. He is then asked to explain
the time dependence of the spectra by information
previously obtained.
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
spectrum of Cr(C6H202h in benzene (broken line).
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
mixture of 40 ml ethanol and 25 ml cone. HC1, the ethanol-HCl
mixture being contained in a beaker. The orange Cr(en)3CI3-
3.5 H20 which separates is filtered out, washed with ethanol,
and air dried.
The catalytic mechanism for this reaction is still
somewhat of an open question, although the formation
1
Reagent grade salt used with further purification.
4
This experiment may be easily expanded to include the prepa-
ration and spectroscopic study of complexes of other ligands.
For instance, the student might prepare a compound containing
the ion Cr(NH3)63 + in order to verify that the spectrum of this
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-
mary role in determining the splitting of the d levels.
102 / Journal of Chemical Education
of trace amounts of a substitutionally labile Cr(II)
species is probably involved.
Tris(%,4-pentanedionato)chromium (III). The method
of preparation is that given in the literature (6).
To 100 ml H,0 are added 2.66 g of CTC'1S-6H20 (0.01 mole)
and, after complete solution, 20 g of urea and 6 g of acetylace-
tone (0.06 mole). The reaction mixture is covered with a
watch glass and heated on a steam bath overnight. As the
urea hydrolyzes to release ammonia, purple crystals of the
complex form. Recrystallize the crude product by dissolving
in a minimum quantity of benzene, filtering, and adding hex-
ane or heptane to precipitate the Cr(CsH702)a.
CrCh 61120. The reagent grade salt consists pri-
marily of the green form of this compound which
is known to have the structural formula (7) trans-
[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.
There are two noteworthy points concerning the
spectra shown in Figure 3. First, the spectrum of
Figure 4. The solid line represents absorption spectrum of an aqueous
solution of CrCl3*6H20 immediately after preparation; the short dashes
represent the same solution after two hours; the dot-dash line represents
the solution after 6.5 hours; and the long dashes represent the spectrum
of CrfHiOjglNOata»3H20.
tris(2,4-pentanedionato)chromium(III) appears to
have only one absorption maximum with steeply rising
absorption in the region of the expected second maxi-
mum. The reason that the second crystal field transi-
tion is not readily detected is that it is obscured by the
intense absorption of light associated with electronic
transitions between orbitals that are primarily ligand-
like in nature and orbitals that are primarily metal-
like in nature. Such transitions are called charge
transfer transitions and commonly are associated with
much stronger absorption of light than are crystal field
transitions.
Secondly, the absorption maxima for Cr(H20)6*+
are relatively small compared to those for Cr(en)3s+
and Cr(C&H702)3. This is qualitatively explained by
the lower symmetry of the ligand arrangement around
the metal in the case of the chelate complexes. Spe-
cifically the chelates lack a center of symmetry whereas
the hexahydrate ion has a center of symmetry. Since
the hypothetical static cent rosy mmetrie ligand arrange-
ment should result in the crystal field transitions being
completely forbidden for the absorption of light by
the electric dipole mechanism (8), we might anticipate
that a complex which is centrosymmetrie would show
weaker transitions even though vibrations always cause
small instantaneous distortions from the centrosym-
metric arrangement.
Experimental Values of 10 Dq of Cr(III) Complexes
Compound 10 Dq (cm"1)
[Cr(H.O)4CyCl-2IUO 15,400“
[Cr(H20)a](N03)s-3H<0 17,100
CrfCJLOds 17,750
Cr( en )3C13 3.5H20
•
21,300
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
spectrum changes with time, so although the spectrum was run
as soon as possible after solution preparation there was probably
a small error due to this.
From the table it is obvious that the 2,4-pentane-
dionato complex lies slightly above water in the
spectrochemical series, so tentatively the 2,4-pentane-
dionato ion may be placed between H20 and NH3
in this series, since we anticipate that NH;; will be
close to ethylenediamine.
Figure 4 shows the time variation of the spectrum
of CrCls 6FFO. The spectra of CrCl3 GH20 illustrate
a point of rather general application in interpreting
crystal field spectra. This is, that even though the
chromium is initially surrounded by four water mole-
cules and two chloride ions, the spectra of the freshly
prepared solution are very similar to the more nearly
octahedral complexes in Figure 3. This is in agree-
ment with what is usually found for such complexes
provided that the two different types of ligands are not
too widely separated in the spectrochemical series. In
these pseudo octahedral cases 10 Dq is found to be
intermediate between that expected for a complex
containing ligands entirely of one type and that ex-
pected for a complex containing entirely the other
type of ligand. In the present case the lower value
of 10 Dq for Cr(H20)4CI2+ compared to that for
Cr(H20)e3+ is in agreement with the lower position of
Cl in the spectrochemical series.
-
From Figure 4 we also see that the spectrum over a
period of several hours transforms to one rather similar
to that of the Cr(H20)e3+ indicating that a rather slow
aquation reaction has gone almost to completion.
The work of Gates and King (9) indicates that for longer
periods of time the CrCl3 6H20 spectra should approach
that of Cr(H20)e3 + quite closely. This was indeed
found to be the case by students who let their solutions
stand for several days before measuring the final
spectrum.
Literature Cited
(1) to Transition Metal Ion
Orgel, L. E., “An Introduction
Inc., New York, I960.
(2) Cotton, F. A. and Wilkinson, G., “Advanced Inorganic
Chemistry'; A Comprehensive Text,” Interscience Pub-
lishers (division of John Wiley & Sons, Inc.), New York,
1962.
(3) Cotton, F. A., J. Chem. Editc., 41, 466 (1964).
(4) Ballhausen, C. J., “Ligand Field Theory,” McGraw-Hill
Book Co., New York (1962), p. 235.
(5) Bailar, J. C. and Work, J. B., J. Am. Chem. Soc., 67, 176
(1945).
(6) Moeller, T., (Editor), “Inorganic Syntheses,” Vol. V,
McGraw-Hill Book Co., New York, 1957, p. 130.
(7) Dance, I. G. and Freeman, H. C., Inorg. Chem., 4, 1555
(1965).
(8) Dunn, T. M., “The Visible and Ultra-violet Spectra of Com-
plex Compounds,” in “Modem Coordination Chemistry,”
(Editors: Lewis, J. and Wilkins, R. G.) Interscience
Publishers (division of John Wiley & Sons, Inc.), New
York, 1960, p. 280.
(9) Gates, II. S. and King, E. W., J. Am. Chem. Soc., 80, 5011
(1958).
Volume 44, Number 2, February 1967 / 103