Chemistry 104B Midterm Exam 2

23 March 2017
9:40 – 11:00 am

Name: _______________________________________SID #_________________________

Notes:
1. Looking at other materials or other students' work during the exam period will result in immediate
confiscation of your exam and further disciplinary action.

2. Write answers in the spaces provided. Do not use the back of the page: ask for additional sheets of paper if
needed, but be sure to secure these to your exam before you hand it in.

3. There are 10 pages to this exam. Take a few minutes to:

i) check that you have all pages;
ii) read through the whole exam to get an idea of where you should focus your efforts before you start writing.

4. You are provided with information on pages 9 and 10 that may be used in responding to questions.

Grading:

Problem Total points

1. __________________________ (4)

2. __________________________ (4)

3. __________________________ (4)

4. __________________________ (5)

5. __________________________ (6)

6. __________________________ (10)

7. __________________________ (14)

8. __________________________ (7)

9. __________________________ (6)

TOTAL __________________________ (60)

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1. (4 points) On the periodic table below, fill in the missing 8 elements.

2. (4 points) Explain the trend of carbonyl stretching frequencies shown below. Limit your
response to 3 sentences or fewer.
Complex νCO (cm-1)
Mo(CO)3(PF3)3 2090, 2055
Mo(CO)3[P(OMe)3]3 1977, 1888
Mo(CO)3(PPh3)3 1934, 1835
Mo(CO)3(NCCH3)3 1915, 1783
Mo(CO)3(NH3)3 1898, 1758

3. (4 points) Why are d-d bands shifted only slightly for [CoX(NH3)5]2+ ions (X = F, Cl, Br, and
I) while charge transfer bands are shifted considerably for this series of compounds?

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4. (5 points) Arrange the following in order of increasing rate of water exchange, and give a brief
rationale for the ordering:
[V(H2O)6]2+, [Cr(H2O)6]3+, [Mg(H2O)6]2+, [Al(H2O)6]3+

5. (6 points) For CoL62+ (where L = a neutral ligand)

a) Show how the free ion ground state term is derived.

b) What is the ground state in a (i) weak and (ii) strong octahedral crystal field? Derivation is not
required.

c) Which d-d transitions might be observed in the UV/vis spectrum in (i) a weak-field complex
and (ii) a strong-field complex?

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6. (10 points) For a reaction of the
following form:

the rate law is:

k1 k2 [ML5 X][Y]
k-1 [X]+k2 [Y]

On the reaction coordinate diagram provided:

a) label ΔG‡ and ΔG0reaction.
b) sketch a new reaction coordinate clearly illustrating the effect of a stronger M–X bond. Would
this change the rate of the reaction? If so, how?

c) Under what experimental conditions will the rate appear to be first order overall? You should
write the new rate law as a part of your explanation.

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7. (14 points) Answer the following questions about the octahedral ion [ReH6]2-.
a) For the H6 LGOs, it can be shown that:
Γred = 6 0 0 2 2 0 0 0 4 2.
This representation reduces to Γ1 + Γ2 + Γ3.
If Γ1 = A1g, and Γ2 = Eg, what is Γ3?

Γ3 =

b) Twelve possible LGOs are shown below. All of the σ-only LGOs for octahedral complexes
are provided as well as several extras that are not correct LGOs. Match the LGOs to the
irreducible representations that contain them. Additionally, state which metal-based valence
orbitals will interact with each set of LGOs based on the symmetry label.
LGO Numbers Metal valence orbitals with same symmetry
A1g
Eg
Γ3

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c) A partially-completed MO diagram is shown below. Empty boxes designate rough areas
where you will draw the appropriate number of missing orbitals. (Assume an energy of -14 eV
for the H- ligands.)
i) Add all missing orbitals at appropriate energies.
ii) Add the appropriate number of electrons.
iii) Label all orbitals (not just those in the boxes).
iv) Draw all appropriate correlation lines between orbitals.

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8. (7 points) Nitrogen monoxide, NO, is a well-known and important molecule. In the context of
transition metal chemistry, NO forms a wide range of complexes similar in some respects to
those of CO. In contrast, the phosphorus analog, PO, is relatively unknown as a result of its
highly reactive nature. In a paper in Organometallics (2000, 19, 4336), the electronic structure of
PO was investigated using computational methods. In the two figures below, molecular orbital
diagrams for two species, the free PO molecule and a (hypothetical) molybdenum complex
(OP)Mo(NH2)3 are drawn.
MO diagram of PO MO diagram of OPMo(NH2)3

By reference to the figures above, answer the following questions:

a) Reduction of PO to PO- results in a decrease in the P-O stretching frequency of 205 cm-1,
whereas corresponding reduction of NO to NO- decreases the N-O stretching frequency by 514
cm-1. What feature of the molecular orbital diagram explains the large difference between these
numbers? In other words, why is the decrease much smaller for PO?

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b) Which d-orbitals on Mo are involved in π-bonding?

c) Is the π-interaction stabilizing or destabilizing? Explain your reasoning.

9. (6 points) Amination of CrCl3 leads only to the pentamine shown below when pure reagents
are used:
CrCl3 + NH3 (l) → [Cr(NH3)5Cl]Cl2
The hexamine [Cr(NH3)6]Cl3 can be made in this reaction, but only when traces of base are
added. Write out the steps for a mechanism to account for the latter observation.

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9
D4h:

Oh:

Td:

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