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Spring 2014 OMET Practice Problem Set

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19 views10 pages

Spring 2014 OMET Practice Problem Set

Uploaded by

eunice.ng1228
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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CHEM 344 Organometallic Chemistry Practice Problems (not for credit)

Spring 2014
Name (print): _______________________ TA name (print): _____________

1) The strength of the C-X bond of halobenzenes Ph-X was explored via computational
chemistry in Chapter 5.
a) Explain the experimental bond dissociation enthalpy values shown below in terms of
bond distance and bond strength.

Ph-X HC-X° (kcal/mol)

127

97

84

67

b) Briefly explain which of the above halobenzenes is the least reactive toward the
oxidative addition of a metal such as Mg or Pd.

1
2) Show all products of the following transmetallation reactions. (Think about the
relative polarities of the C-M bond in the starting material and the main product. The
periodic table of electronegativity values for each element attached to this problem set
may be useful.)

2
3) Suzuki-Miyaura coupling reactions typically occur between aryl or alkenyl halides and
an arylboronic acid. An example of such a reaction is shown below for the synthesis of
the food flavoring compound trans-anethole (trans-1-methoxy-4-(1-propenyl)benzene).

a) Propose a synthesis of 4-methoxyphenylboronic acid starting from phenol (it involves


more than one step). Recall that trimethylborate, B(OMe)3, reacts as an electrophile
toward Grignard reagents. Show all isolated intermediates/products formed. You do
not need to give a mechanism for the individual steps.

3
b) Complete the catalytic cycle for the Suzuki-Miyaura coupling reaction shown above,
drawing the appropriate reagents and products of each of the three labeled steps. The
role of KOH in the reaction will be discussed in the Suzuki pre-lab session next week.

4
c) Draw and label the full catalytic cycle for the Stille coupling of 2-iodotoluene and
tributyl(vinyl)stannane shown below.

5
4) Draw the balanced reaction for the formation of isopropylmagnesium bromide in
diethyl ether and show the charge distribution along the carbon-metal bond. Explain
why diethyl ether and THF are common solvents for the generation of Grignard
reagents.

6
5) Ruthenium- and molybdenum-based complexes are used as catalysts for alkene
metathesis reactions. One such Ru-based complex, the Grubbs 2nd generation catalyst
(G2), is shown below. The complex features both an N-heterocyclic carbene ligand and
a tertiary phosphine ligand (Cy = cyclohexyl group).

Ruthenium metal alone does not catalyze alkene metathesis reactions. Give 3 reasons
why metal-ligand coordination complexes such as G2 are more useful than elemental
metals for organometallic catalysis.

7
6) Draw the products of the following Pd-catalyzed reactions.

8
7) Each of the compounds a) through d) can be synthesized by either a Grignard
reaction or by a Pd-catalyzed coupling reaction. The C-C bond generated by the
organometallic reaction is shown in bold.
Draw starting materials, reagents, catalysts, etc. that could be used to form the bold C-
C bond in each compound and name each reaction used to form each bold bond.

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Periodic Table – Pauling Electronegativity values

Electronegativity

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