PROBLEM - SET - 6 - Answer

CHEM 5000 Homework 5 (Due Nov.
3rd)
1. A mechanism for alkene arylation catalyzed by Pd(II) is outlined
below. The isotope effect kH/kD was found to be 5 when benzene-
d6 was used. There was no isotope effect when styrene-β-d2 was
used. Which steps in the reaction mechanism could be rate
determining, given this information on isotope effects?
Answer: The first step must be rate determining, since the aromatic hydrogens
exhibit a primary isotope effect, whereas there is no isotope effect for
elimination of hydrogen from the styrene reactant, which occurs in Step 3. Step
2 would not be expected to exhibit a primary isotope effect because the aryl
hydrogens are not directly involved in the reaction, but should exhibit a
secondary isotope effect for styrene-β-d2.
2. The Cannizzaro reaction is a disproportionation that takes place in
strongly basic solution and converts aromatic aldehydes to the
corresponding benzyl alcohol and sodium benzoate.
2ArCHO+NaOH −→ ArCH2OH+ArCO2Na
Several mechanisms, all of which involve a hydride transfer as a key
step, have been postulated. On the basis of the following information,
formulate one or more mechanisms that would be consistent with all
the data provided. Indicate the significance of each observation with
respect to the mechanism(s) you postulate.
a. When the reaction is carried out in D2O, the benzyl alcohol
contains no deuterium in the methylene group.
b. When the reaction is carried out in H218O, both the benzyl
alcohol and sodium benzoate contain 18O.
c. The overall reaction rate is given by the expression
Rate = kobs[PhCHO]2[−OH]
d. The rates of substituted benzaldehydes are correlated by a
Hammet LFER with ρ=+3.76.
e. The solvent isotope effect kD2O/kH2O = 1.90
Answer: The mechanism is believed to involve rate-determining hydride
donation from hydrated benzaldehyde. The lack of exchange with solvent
protons indicates that it is the formyl hydrogen that is transferred. Reversible
formation of the aldehyde hydrate and its conjugate base accounts for the
appearance of 18O in both products. The third-order rate expression is also
consistent with involvement of the hydrate. The role of aromatic substituents
could be complex. The extent of hydration and the reactivity of the aldehyde
to hydride transfer would be favored by EWG substituents. On the other hand,
the hydride transfer itself would be retarded by an EWG in the hydrate. The
positive ρ indicates that some combination of the former two factors must be
dominant. The inverse isotope effect rules out rate-limiting O−H bond-
breaking and is consistent with the greater nucleophilicity of −OD compared to
−OH. The observations are consistent with a mechanism in which the
aldehyde hydrate acts as the hydride donor.

3. In the following reactions substituent X was varied between
electron donating and electron withdrawing. If you use the usual σ
values, do you expect a positive or negative ρ value for each
equilibrium? Should each reaction be more sensitive or less
sensitive to the X substituent than benzoic acid? Explain your
reasoning for each answer.
Answer: Like the benzoic acid reference reaction, both of these reactions
are acid base equilibria. In both cases, the reactant is neutral and the product
is charged. The first reaction, with a negatively charged product, should have
a positive ρ value, just like the ionization of benzoic acid. The product of the
second reaction is positively charged, so in this case a negative ρ value is
expected. In the enolate product of the first reaction, one of the two resonance
structures places the negative charge on the C bearing the X group. Since
resonance in benzoate does not bring the charge to the C bearing the X group
(or even into the aromatic ring at all), the enolization reaction shown should
have a ρ value much greater than 1. (Due to the strong resonance effect, the
inductively based σ values might not produce a linear plot for the enolization
and σ- values might give a better result.)
4. Taking the following equation as an example, its KIE is 0.85.

What does this mean?
Answer: When using mixtures of deuterated aldehyde and aldehyde as

substrates under standard conditions, a significant inverse secondary isotopic
effect (KIE = 0.85) was observed. This result suggested that partial
rehybridization of the carbonyl carbon from sp2 to sp3 and insertion of the
carbonyl(2a) into the aryl species(1a) were the rate-determining steps of the
reaction.

PROBLEM - SET - 6 - Answer

Uploaded by

Copyright:

Available Formats

PROBLEM - SET - 6 - Answer

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

PROBLEM - SET - 6 - Answer

Uploaded by

Copyright:

Available Formats

CHEM 5000 Homework 5 (Due Nov.

aldehyde hydrate acts as the hydride donor.

4. Taking the following equation as an example, its KIE is 0.85.

Answer: When using mixtures of deuterated aldehyde and aldehyde as

You might also like