Allowed and Forbidden d-d Transitions i n C r ( o ~ a l a t e ) ~ ~ -

Introductorv treatments of electronic structure and s ~ e c t r of

a transition metal comnlexes usuallv cite the small molar

a good laboratory introduction to transition metal chemistry.

Experimental
The synthesis of K3Cr(oxalate)3.3HzO is described in Inorganic Synthesis ( 2 ) and,
with modifications, in a recent laboratory manual (3).Both preparations work well, though n-' .I@
sometimes the reaction mixture does not spontaneously warm up and must be heated. The x 20

crude product can be recrystallized from water by reducing the volume or by adding eth-
anol. The recrystallization should be done quickly with minimal heating to minimize
aquation of the complex. I ':
Visible spectroscopy of M solutions in H 2 0 using a l-cm path-length cell yields
spectra with convenient ahsorbance for the allowed hands and a clearly visible forbidden
band (see figure). i i

Assignment of Transitions In the Cr(oxalate),'- Spectrum

I
band maximum
nm cm-' r(M-' em-') assignments

'using A = 17,500 c m ' . B = 660 cm-' late)? in aqueous solution at r o o m

temperature.
Interpretation
Reference to the d3 Tanahe-Sugano diagram (4) rev&& that the lowest energy electronic transitions would be expected
to be from the 'A2 ground state t o thedT2 and 'TI excited states (spin allowed) and to the 2E, ZT1, excited states (spin
forbidden). The transitions can be assigned as given in the table by finding the value of ligand field strength far which the
observed peak maxima fit the energy levels in the Tanabe-Sugano diagram.
Discussion
Observation of both allowed and forbidden transitions in room temperature spectra of dissolved transition metal
complexes is relatively rare. C r ( o ~ a l a t e ) ~
happens
~- to be a particularly favorable case which is also convenient for study
in undergraduate laboratories. Although the fit of the spectral data to theTanabe-Suganodiagram is, in general, an iterative
procedure, there is a feature for d3 which lends extra confidence to the result: for the ease of a d3 ion the energy of the first
allowed transition gives the ligand field strength Ao directly (5).
Literature Cited
(1) (a1 Cotton, F. A..and Wilkinson.G.. "Advanced InorganieChemistry," 3rd Ed., Intcracienee, New York, 1912, p 578. (b) Heslop, R. B., and Jones, K.,"lnorganie
Chemistry? Elsevier, New York, 1976, p 160. (c) Purmll, K. F., and KoU,J. C.. "Inorgsnie Chemistry," Saunders, Philadelphia, 1977, p 564.
12) Rai1ar.J.C.. Jr..and Joner,E. M..lnorg. Synfh. 1.37 (1939).
(31 Nelson,J. H.,snd K e m r K.C.,"LaboratorvEx~rimentthrBmmmdLeMey.Cbemistry:TheCentralScienee~P~ntim-Hell. E n r l e w d Cliffs,NewJe~y,
1977. p 297.
(41 la) Hall. L.H.."Croup T h w r y m d Symmetry inchemistry? Mffirsw-Hill.NewYark, 1969, p 322. (b) Cotton, F. A.."Chomieel Applications of GmupTheow?
2nd Ed., Wiley-Interscience. New Yark, 1971, p 266.
(6) Ref LC, p 667.

S. S. Eaton T. D. Yager
University of Colorado at Denver G. R. Eaton
Denver, CO 80202 University of Denver
Denver, CO 80208

Volume 56. Number lo, October 1979 / 635