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I– < Br– < OCrO32– chromate < Cl– SCN– < N3– < F– SSO32– thiosulfate
urea (O) < OCO22– carbonate < OCO2R– carboxylate < ONO– OH– < OSO32–
sulfate < ONO2– nitrate < O2CCO22– oxalate (bidentate) < H2O < NCS– < glycine
EDTA4– < pyridine NH3 < en < SO32– < bipy < o-phen < NO2– < PPh3 <
Cp < CN– < CO
The magnitude of o increases by a factor of about 2 as one moves from the halides to
CN– in the spectrochemical series.
70 2A
1g
4T
60 1g
50 4T
2g
E/B
40
2F
2T
2g
30
2T
1g
20 2E
2G g
4P
10
4F
4A
0 2g
0 10 20 30 40 50
o/B
Figure 1
selection rules. The states in order of ascending energy are labeled 4T2 (two electrons in
the t2g and one in the eg), 4T1, and another 4T1 (one electron in the t2g and two in the eg).
The energy separation between the two lowest energy levels, 4A2 and 4T2 is o. This
absorption band will be the one at the longest wavelength (lowest energy) in the
spectrum.
Hazards
Experimental Procedure.
I. A. tris(2,4-pentanedionato)chromium(III)
B. tris(ethylenediamine)chromium(III)
D. hexakis(urea)chromium(III)
2.7 g CrCl3·6H2O and 3.6 g urea are dissolved in 10 mL of distilled water and a
few drops of 3 M HCl is added. The solution is heated on a steam bath until a
crystalline crust forms. The slurry obtained is dissolved in the minimum of water
at 50-60 oC and rapidly filtered. The salt crystallizes as light green needles.
Allow the solid to dry under vacuo. Transfer to a labeled vial. The formula is
[Cr(CH4N2O)6]Cl3.
E. hexakis(isothiocyanato)chromate(III)
Obtain the absorbance spectrum for each complex. Determine the longest wavelength
maximum nanometers. Convert the wavelengths (which correspond to o) into
wavenumbers (cm–1) using the following relationship:
Also calculate B (where possible) and comment on the nephelauxetic effect of the
ligand. Finally, determine from Beer’s law and relate the magnitute to the symmetries
of the complexes.
References
1. This experiment is adapted from: Szafran, Z.; Pike, R.M.; Singh, M.M.
“Microscale Inorganic Chemistry: A Comprehensive Laboratory
Experience”, 1991, John Wiley & Sons, New York, NY, pg 248 and
Bailer, J. C.; Jones, E. M. Inorg. Synth., 1939, 1, 37.