Electronic Spectra of cis and trans Disubstituted
Octahedral Chromium(lll) Complexes
An Advanced Inorganic Chemistry Experiment
Francesc Teixidor and Jaume Casabol
Universitat Autonoma de Barcelona, Bellaterra, 08193 Barcelona, Spain
Andreu Solans
Productos UHPON S.A., Rubi, Barcelona. Spain
Electronic spectroscopy is a valuable tool used routinely in
coordination chemistry research laboratories. For a long
time it has been one of the most classical and powerful
techniques available to elucidate the fine details of coordina-
tion compound stereochemistry. It is well known that the
understandine of the stereochemistrv of amine comnlexes of
chromium(llfi, cobalt(III), or ruthe&un(11) was almost en-
tirelv based on their electronic soectra.
A."B. P. Lever ( I ) says
Whilst many physical techniques play their part in the elueida-
tion of the geometric and electronic structure of a metal complex,
a study of the electronic spectra can often provide the most
detailed information. In the spectrum we see a map of the energy
bands within the molecule-the trick is to learn how to read this
map.
Since visible and UV spectrophotometers are now very com-
mon in teaching lnboratorieii] in our opinion ir is veriinter-
esting to let thestudents learn ah0111the largr analytical and
structural elucidation powers of this technique.
Among the most dramatic examples that show the power
of electronic soectra to elucidate stereochemistm are the
spectra of ris and trans diauhitituted octahedral romplexes
ol Crtllli or Cu(II1).whichdis~laswell-known oattrrns. I'se
of these also shows'the powe;ofthe group theory in quan-
tum mechanics. At present,, elementary group theory is part
of the inorganic chemistry curricula of most universities.
In our department the students spend part of their labora-
tory time in synthesizing of cis- and trans-[CrFz(en)z]Cl,
recording their spectra, and interpreting them. By doing this
they get first-hand knowledge about cis/trans isomeric
chemistry, learn about electronic spectra, and study the in-
tricate differences between cis and trans electronic spectra,
which are currently neglected in almost all textbooks. Usual-
ly, only trans isomers are explained, apparently because they
fit elementary group predictions and the cis isomer spectra
do not.
Furthermore, we think the preparation of trans- and cis-
[CrF2(en)2]CIcomplexes is also interesting from the synthe-
sis point of view since they are both formed during the
reaction and their separation is easily achieved because of
their different solubilities. It is not clear, a t present, whether
both isomers really are formed simultaneously or one of the
isomers is being isomerized to the other during the reaction.
The easiness of trans-cis isomerization in this kind of com-
plex is well known. On the other hand their electronic spec-
tra are very typical, showing all the details expected for
-
them. The cation trans-CrFz(en)2+ is of particular interest
because of the large splitting of the (AQ (Tzg and 'Azg
'TI, bands (2).
- bv charae-transfer bands. The cis and trans octahedral di-
' Author to whom correspondence should be addressed.
trans-[CrFz(en)2] CI (3)
A solution of 30 g (0.11 mol) of chromium(II1)chloride hexahy-
drate in 100 mL of water was placed in a 400-mL polyethylene
beaker and diluted with 24 g (0.6 mol) of a 48%solution of hydraflu-
oric acid. The beaker was packed in ice and 100 g (1.58 mol) of
aqueous 95% ethylenediamine was added dropwise over 1 h. After
the addition of the ethylenediamine was completed, the dark red-
purple solution was heated for 2 h on a steam bath to complete the
reaction. The solution, which had darkened in color during the
heating, was transferred to an evaporating dish, and the excess
water was removed by heating for an additional 2 h at 90-95 'C.
During this time a crustwas formed on the surface of the liquid, and
this was broken up frequentlyduring the late stages of the evapora-
tion. At the end of the 2 hours the reaction mixture was cooled to 10
OC in an ice bath and filtered.
Caution: All work should he done in a hood. The manipulation of
95%ethylenediamineor 48% HF solutions is potentially dangerous;
the latter can seriously damage the skin.
The crystals that had precipitated were collected, washed with
100 mL of EtOH followed by 100 mL of acetone, and air-dried.The
above procedure yielded 15.5 g (56%)of reddish orange crystals.
T o the mother liquor from thes!nthe+ of Iran? isomer (150ml.l
were a d d ~ d i.n i,rder, dry \leOH t3OO ml.,, Mr?CO (300 mL,, nnd
Et.4<200ml.) u i t h viaorousrirrinr, whereupon a pinksolid slowlv
began to precipitate. Caution: All procedures involving ether are
hazardous. Oecasionallv. the .orecinitation
. had to he started bv
scratching the henkrr's walls. In n r d ~ ro
r assure complete prrripita-
rion, t he mixture uns kept at h w temperature (freezer)for 2 h. 'l'hr
solid wuifilterednnd naihed withdry hlr,C'OandFt?Oanddried in
a dry air stream to avoid the formation of resins or gums.
Electronic Spectra
It is convenient to record the electronic apeetra in aqueous solu-
tion and to record the spectra of both isomers superimposed at the
same molar concentration to show their similarities and differences
in hand positions and molar ahsorptivities. Alsoit would be instruc-
tional to record the spectrum of the initialsolution since it displays a
cis pattern, although cis and trans species are present in the solu-
tion.
Theory
Octahedral chromium(1II) complexes exhibit three spin-
allowed transitions (5) from the ground state 'AA to the
excited states4TQ(F),4T1p(F),4Tlg(P).It is well known that
onlv the first two transitions are aenerallv dis~lavedin the
spectrum because the highest in energy is in fait overlapped
sibstituied complexes belong to CPUandD4hsymmetry point
croups,
- . respectively, but, from the view of the electronic
environmedt around the metal ion, both symmetry groups
are in practice the tetragonal one, Ddh. This fact is not gener-
ally recognized and is neglected in almost all textbooks, but
it is well explained in Ballhausen's classic Introduction to
Ligand Field Theory (6).
Volume 64 Number 5 May 1967 461
 The electrostatic potential, V , a t the point (x,y,z) due to Spectral Data and Assignments
two point charges, ql and 92, placed on the x axis a t a dis-
tance f a from the center of the coordinate system, is given complex Ion h (nm)' "2 (nmIb ~nm)~
by CrFBs- 671 441 291
Cr(en)2+* 458 351 -
~IsCrF~(en)~+ 517 378 235
transCrFden)f 530' 3979 248"
In this expression Pz(x) and Pa(x) are the first two even 485' 3511 229"
Legendre functions and r the radius vector of the point
(xY,z).Notice that only the sum of ql and qa isof importance
for the crystalline field potential. In other words the crystal-
line potential for an octahedron can be written as the sum of
three contributions, each of them containing the sum of the
axial electronic charges.
If the sum of the charges on the x, y, and z axes are pz, py,
"B,, -
"B1*-'E0
'EgIOmdcomponem of u,.
(Olnl component of u,.
and p, and if p, = II, = pz, the complex is said to have a cubic "B,, -
"'B,, -'A,,(D,d mmponem of vs; calculated Com reference 2.
component of u,.
crvstalline field. If u, = u, # u,. the comnlex is said to have a
tetragonal crystall& fikfd. 0 r i f p, # py.# p,, the complex is
said to have a rhombic crvstalline field. I t is nossible to
-
J's,.-'A,, lD,d component of u,.
"'B,, 'E0(D4d component of nS: calculated from reference 2.

define a tetragonal contribution, VT,to the octaKedra1 crys-

talline field, f(x,y,z), as:
nal contribution with respect to trans isomers and generally
the splitting is not observed in the spectrum (eq 1). The
minus sign means that the order of splitting in the energy
levels would be inverted in both isomers.
and Thus, in theory our three-band spectrum of an octahedral
d3 complex, becomes a six-hand spectrum, but all six bands
are rarely seen. I t is generally true that the lowest energy
therefore spin-allowed transition is most susceptible to the effects of
lower symmetry and the highest energy one is generally
overlapped by charge-transfer hands.
consequently, for trans-MA4B2 Results and Dlscusslon
PZ = %
A' Reported in the table are the electronic spectra of both
P7 = %A cis- and trans-CrFde&+ isomers (3.4) and the band assien-
P, = 248 ments as they are givenby ~ u b i c kkt ; al. based on a sinGe-
crystal, polarized electronic spectral analysis (2).
and for cis-MA4B2 The rule of "average environment" (5)relates the pseudo-
octahedral mixed complex CrF2(enIzf with CrF$ and
C r ( e n ) ~ ~By
+ . applying this rule we may obtain an approxi-
mate value of 10 Dq for ci~-CrFz(en)2~+ and predict its spec-
trum in this fashion:
where, q~ and q~ are the point charges due to the ligands A
and B. As can be seen, both isomers have equal values for p,
and py and one different value for pz so they belong to the
same D4kelectronic symmetry point group. Furthermore, for and
the trans complex

This is in good agreement with the experimentalvalue of 517

and for the cis complex nm for the c i ~ - C r F ~ ( e ncomplex.
)~+
Using the graphic methods outlined in several textbooks
or in reference 5, one can obtain the B value, which is 674
And -
cm-I. Using these B and Dq values for cis-CrFz(en)2+, the
highest energy transition, 4A2g 4T2g(P), is calculated at

that overlap and obscure this d d transition.

Literature Cited
-
235 nm. In this region there are strong charge-transfer bands

From these expressions i t may be seen that 1. LFYFI,A.B.P.Cmrd. Ckem.Reu. 1968,3.119.

2. Dubieki.L.;Hitchman.M.A.:Day.P.Inorg.Ckem. 1970.9. 188.
3. Vsughn.J. W.:Stvsn,O.J.: Magnusson. V. E.lnorg. Chem 1968,7,736.
4. Cssabb,J.;Solans.A.;Resl,J. J.Synlk.Reoct.Inorg. Me1.018. Chorn. 1983.13.835.
Both cis and trans isomers should show the tetraeonal 6. Figgi~,B. N. Intmducfian l o Llmnd Fields; Intorscience: New York, 1966.
6. Ballhausen, C. J.lnlroducfion to LigondPidd Theo~y; MeGiaw-Hill: New York, 1962.
splitting of the octahedral transitions, but only the trans 7. J o r g e n m , C. K. A b a o r p t i i Spadm and Ckrmieol Bonding in Complrier:Pergamon:
isomers exhibit it. The cis isomers have only a half tetrago- London. 1962.

462 Journal of Chemical Education