Académique Documents
Professionnel Documents
Culture Documents
Introduction
Certain types of isomerism could not have been foreseen by the classical methods
used by Jrgensen and Werner during their long-standing dispute over the
coordination theory. Often these could only be determined by modern
spectroscopic and structural methods, although these in themselves have some
serious pitfalls (see additional question #5). An example of such a phenomenon is
the linkage isomerism of the nitrite ligand, NO2-. This bent ion has lone pairs of
electrons on the oxygen and nitrogen atoms, and can coordinate to metals via either.
With metals of suitable intermediate hardness, both forms of coordination may be
observed to the same metal fragment. The structures of the two complexes prepared
in this laboratory are depicted in Figure 2-1.
O
O
++ N O
O N
H3N 3 H3N
Co Co
H3N NH3 H3N 3 NH3
NH NH
NHNH
Cl-Cl-
3 3
Figure 2-1 Three-dimensional representations of the linkage isomers prepared in this experiment.
Instructional goals:
Pre-lab exercise
1. Write balanced equations for all the steps in parts 1 and 2 of the synthetic
procedure.
2. What are the point groups of the structures in Figure 2-1?
3. Write out the Lewis structure of the nitrite ion, identifying the lone pairs
used in the two coordination modes.
4. What range of IR frequencies do you need to record to get the data required
for this experiment? How will IR distinguish the two isomers? Give
specific details.
5. Map out the timing of your afternoons work. Use free gaps of time to do
other operations. Be realistic in the time allotted for each operation!
Procedure
After all the peroxide has been added, place the evaporating dish on a steam bath
in the hood. Heat with occasional stirring for 15-30 minutes(do not allow to dry).
The contents should be a brownish thick slurry. Rinse the paste into a 250 mL
beaker containing 100 mL of 3M HCl and heat the solution with stirring for 10
min. Allow to cool and filter the precipitate using a Bchner funnel and trap. Wash
the precipitate with three 10 mL portions of ice-cold water, then with three 10 mL
portions of acetone, and suck dry.
Characterization
Measure the melting point of all three products. Calculate the percent yields and
obtain their IR spectra as KBr pellets. Since chloride ions give no IR signals, and
the Co-Cl bond only a weak stretching band, the spectrum of the chloropentammine
complex can be use to separate the bands due to the nitrite group from those due to
the ammine ligands. Compare the data with literature values.
Study the effects of (i) time, (ii) heat and (iii) ultra-violet light on the solid samples
of the two isomers (see ref. 4-8). This can be conveniently done on the KBr pellets if
sufficient care is taken with them. For example, prepare 2 KBr pellets of the ONO
complex and the NO2 complex. After obtaining initial spectra, leave one of each in a
desiccator for 1 wk. Heat the others in an oven at 100 C for several hours between
measurements. Continue this process until no further changes in the spectral patterns
are observed. For (iii), several hours exposure to an intense UV light source may be
required in order to see changes. HINT: It is a waste of paper to print all the spectra
you measure; use the multiple spectra option to compare sequential spectra on the
computer screen. Print only definitive spectra, or combine several spectra showing
the growth and decay of peaks on a single sheet of paper.
This study should be done with sufficient care that you can unequivocally describe
the effect of all three processes on the two isomers. Use IR spectroscopy to monitor
the changes. N.B.: It is not necessary to print out all the IR spectra you measure,
e.g. if heating the sample causes only a partial change, return it to the oven longer
and re-record the spectrum at a later time.
Report
Hand in your product as well as all original spectra. Discuss the IR spectra with
respect to the identification of the linkage isomerism. Present the results of your
solid-state reaction studies, documented by appropriate IR spectra. Your Discussion
should address at least the following points:
1. What is the structure of each isomer?
2. Which ligand is observed in the IR spectrum? What is the symmetry of this
ligand in each compound? Use group theoretical arguments to assign the
spectral bands of the two isomers.
3. Discuss the base-hydrolysis mechanism as it relates to the purification step
in Part I; discuss the chemical principles used in the conversion of the
purified complexes into the products of Part II. Explain the origin of any
mixtures observed in the products.
4. Discuss the formation of the two isomers in this experiment in terms of
possible thermodynamic and kinetic controlling factors (see ref. 4).
5. Discuss the photochemical reaction observed in this experiment.
Background on photochemistry of transition metal compounds is provided in
the course text, p. 492ff.
References