EXPERIMENT 4

Synthesis, Spectroscopic, Electronic, and Magnetic

Properties of Some 3d Metal Complexes
OUTPUT
Answers-to-questions report / data sheet

POINTS OF DISCUSSION (PART 1)

Synthesis of 3d Metal Complexes

1. For all complexes. Rationalize the synthetic design of each of the coordination compounds
synthesized. Write down chemical equations for each relevant step. Rationalize the choice of
precursor salts.
2. For all cobalt complexes. Explain why Co(III) complexes are usually prepared from Co(II)
precursors, instead of directly preparing them from Co(III) precursors.
3. For all complexes. Determine the percent yield of each product. Discuss possible factors that could
have reduced the yields of the synthesized complexes.

Characterization: UV-Vis Spectroscopy

4. For all complexes. Using Tanabe-Sugano diagrams, assign transition to the observed peaks in the
UV-Vis spectra of the complexes. Calculate for the ∆o and the Racah parameter B for each
complex. Show complete solutions in your calculations.
5. For all cobalt complexes. Discuss how changing the ligand, while keeping the same metal, affects
the value of ∆o. Cite specific examples and values from your data. Provide a spectrochemical series
of the ligands based on the UV-Vis spectroscopy experiment you performed. Compare this with the
spectrochemical series given in your textbooks.
6. For all oxalate complexes. Discuss how changing the metal, while keeping the same set of ligands
L, affects the value of ∆o. Cite specific examples and values from your data. Provide the Irving-
William’s series of the metals based on the UV-vis spectroscopy experiment you performed.
Compare this with the series found in your textbooks.
7. Zinc ion does not exhibit the same behavior as the rest of the transition metals. For example, among
the first row transition metal species, only zinc ion is colorless. Explain why this is so.

Characterization: FTIR Spectroscopy

8. For all complexes. Refer to the IR spectra. Assign the important peaks in the IR spectrum of each
complex. Then, compare the stretch frequencies (C=O and C-O for oxalate, N-H for ammine and
en, N=O and N-O for nitro and nitrito complexes) of the complexed ligand to that of the free ligand
(as observed in K2C2O4, NaNO2, and NH4Cl). Explain the observed IR shifts in the above bond
stretches.

POINTS OF DISCUSSION (PART 2)

Linkage Isomers
1. For complexes 3b and 3c. Explain how the concepts of thermodynamic and kinetic control were
applied to the syntheses of nitrito (3b) and nitro (3c) complex isomers.
2. For complexes 3b and 3c. Discuss how the IR spectra can be used to distinguish the nitrito (3b)
from the nitro (3c) isomer.
3. For complexes 3b and 3c. Displacement of chloride in complex 3a by nitrite may yield two possible
products: the nitrito and nitro isomers. One is produced by kinetic control, the other by
thermodynamic control. Apply molecular orbital theory to rationalize the observed reactivity.

Characterization: Magnetic Susceptibility Measurement

4. For all complexes. Refer to the magnetic susceptibility measurements. Identify which of the
complexes are paramagnetic and diamagnetic. Then, calculate the experimental μS for the
paramagnetic complexes. From the experimental μS, estimate the number of unpaired electrons, and
identify the oxidation and spin (high or low) state of each complex. Then, account for the observed
discrepancies. Show complete solutions in your calculations.
5. Discuss how the instrumentation in Evans balance works in measuring the magnetic susceptibility.
Compare it with the instrumentation of the Gouy method. Display the relevant schematic diagrmas.
Then, discuss the advantages and disadvantages of both methods.
6. Discuss why paramagnetic complexes give large positive readings in the Evans balance, whereas
diamagnetic complexes give small negative readings.

Resolution of [Co(en)3]3+
7. Draw the lambda and the delta isomers of [Co(en)3]3+.
8. Rationalize each step in the resolution of [Co(en) 3]3+, especially the role of L-(+)-tartaric acid.
9. Explain why iodide is preferred as the counterion in the resolution procedure.
10. Explain why heating must be controlled in the resolution procedure. Explain what would happen
when the reaction workup was overheated.
11. A common problem in resolution is that the target products do not crystallize out. Cite techniques
that can improve the chance of crystallization without racemization.

Characterization: CD spectroscopy
12. Interpret and compare the CD spectra of the two optical isomers, as well as the racemic mixture.
Identify the wavelengths where peaks and valleys occur, and account for their existence.
13. Discuss the theory behind CD spectroscopy, and why it can be applied to distinguishing optical
isomers. Also, discuss the instrumentation used in CD spectrometers and how it generates the CD
signals.