5.

03 Exam 5
Christopher C. Cummins
April 19, 2010

Instructions

Clearly write your name at the top of this front page, but otherwise do not write on this front page
as it will be used for scoring. This exam is closed-book and no calculators or electronic devices
may be employed. There are five sections so please read over the exam before you begin and expect
to take on average ten minutes per section. Read all questions carefully before writing down any
answers. Enjoy the material!

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1 Ligand Field Stabilization Energy
The questions for this section are worth 4 points each.
1. At what four (θ, φ) values does a dxz orbital wavefunction attain a maximum absolute value?

2. Show that dz2 and dx2 −y2 have the same energy in a tetrahedral complex by considering the
values of θ and φ at the positions of the ligands. Explain your reasoning. Note: the equation
for dz2 is 3cos2 θ − 1, while that for dx2 −y2 is sin2 θcos2φ.

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3. Explain why it is that low-spin tetrahedral complexes are extremely rare, in contrast to the
situation for octahedral complexes.

4. On going from d0 to d5 (high-spin octahedral case), there is a maximum in ligand field stabi-
lization energy, LFSE, at d3 . What is the magnitude of the LFSE for the d3 system in units
of ∆o ? Explain how this number can be arrived at.

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5. With reference to the following graphic showing hydration enthalpies for [M(H2 O)6 ]n+ ions,
what must be n, the value of the charge on the ion?

6. To what do the filled and open circles correspond in the above plot?

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2 Spectrochemical Series
The questions for this section are worth 4 points each.

1. The spectra below are for pseudo-octahedral copper(II) complexes with an O6 , an N2 O4 , and
an N4 O2 set of donor atoms. Based on inspection of the spectra, which type of donor atom
generally lies higher in the spectrochemical series, O or N?

2. Except for consideration of Jahn-Teller effects, spectra for pseudo-octahedral copper(II) com-
plexes are as simple as those for what other 3d ion?

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3. What is the ligand that is typically listed highest in the spectrochemical series? Give two
reasons why this ligand gives rise to such large values of ∆o .

4. Is there a red spectral shift or is there a blue spectral shift when en is added to a solution
containing aqueous nickel(II) ion? Explain what is happening chemically and why the spectrum
shifts as it does.

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3 Tanabe-Sugano Diagrams
The questions for this section are worth 4 points each.
1. For a nickel(II) complex three bands are observed at energies of 8000, 13200, and 22800 cm−1 .
what is the value of ∆o ? Shown below is the Tanabe-Sugano diagram for the d8 case.

2. Using the values from the preceding question, what is the approximate value of ∆o /B that is
indicated by the ratio ν2 /ν1 ?

3. Given the value of ∆o /B you obtained in the previous question, what value of B 0 is indicated?

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4. In the Tanabe-Sugano diagram for the d8 case, it can be seen that two of the triplet states
are curved due to configuration interaction. Which triplet states are these, and what are the
configurations that give rise to them?

5. How many spin allowed bands are there for a manganese(II) complex in the case where ∆o /B
is about 20?

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4 Magnetism
The questions for this section are worth 4 points each.

1. Upon addition of en to an aqueous solution of manganese(III) ion in an NMR tube configured

for Evans’s method magnetic susceptibility measurements, measurements of ∆ν taken as a
function of time show that the magnitude of ∆ν is decreasing substantially. To what values
of µ should the initial and
pfinal values of ∆ν correspond? Assume that spin-only behavior is
observed, wherein µs = g S(S + 1).

2. When making an Evans’s method determination of the molar magnetic susceptibility of a

dissolved substance, what are the three quantities needed in order to do the calculation?

3. After carrying out a calculation of the molar magnetic susceptibility as referred to in the pre-
ceding problem, correction for diamagnetism must be carried out in order to obtain χcorr
M (this
is the same thing as χP , the paramagnetic susceptibility). Is the value of the sample’s dia-
magnetism (obtained using Pascal’s constants or otherwise estimated) added to or subtracted
from the molar magnetic susceptibility in order to arrive at χcorr
M ?

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4. What is an approximate relationship between the molecular weight of a substance and its
diamagnetic susceptibility, χD ?

√
5. Using the relationship µ = 2.84 χP T , what is the approximate molecular weight at which the
measured magnetic susceptibility of a substance having two unpaired electrons per molecule
goes to zero at 298 K?

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5 Single-Molecule Magnets
The questions for this section are worth 4 points each.

1. To what point group does the molecule [Mn12 O12 (O2 CCH2 Br)16 (H2 O)4 ] belong (see graphic)?

2. In the case of [Mn12 O12 (O2 CCH2 Br)16 (H2 O)4 ], how many manganese ions are present for each
of the oxidation states +2, +3, and +4?

3. For [Mn12 O12 (O2 CCH2 Br)16 (H2 O)4 ], show how the result from the preceding question leads
to the observed value of S.

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4. Using single-crystal measurements, Sessoli et al. showed that the magnetic susceptibility for
[Mn12 O12 (OAc)16 (H2 O)4 ] measured parallel to the crystallographic c axis was about fourteen
times greater than that measured perpendicular to the c axis. Note that the crystallographic
c axis is aligned with the highest order principal rotation axis of the cluster molecules. This
anisotropy of the magnetic susceptibility is attributed to what structural attribute of the
manganese(III) ions within the cluster?

5. The presence of a large, negative, value for D means that in the absence of an applied mag-
netic field only two states are populated at low temperature for the molecular magnet of the
preceding problem. Which are these states?

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Structure Yes D h

linear
linear Yes i

Special Group
Elements
No C v

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Linear or Yes
low symmetry
Yes Cs

single element
Yes Ci
No
i
No C1

icosahedral
Yes Ih
highly symmetric
Sure? More than one Yes Yes
(octahedral, 6C5 i
Yes Cn axis of C3
tetrahedral,
or higher? No I
icosahedral)
No

High Symmetry
Yes Oh

octahedral

Elements
No 3C4 Yes i
No O
No

Yes Td
3S4

Tetrahedral
Yes Th
No
i
No T

Normal Yes Yes Yes Dnh

symmetry C2 Cn

Elements (most common)

Dihedral
Yes Dnd

Normal Symmetry
No
No
No Dn

Yes
Cnh
Single Axis

No
Yes
v Cnv

No
Yes S 2n
S2n
No Cn

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