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Chem 153 Problem Set 1

This document contains instructions for Problem Set 1 assigned by Professor Yuki Oyama for Chemistry 153. Students are to [1] solve problems related to isovalent hybridization and molecular charge distribution, and [2] explain observations related to resonance. The problem set is due by March 6th in PDF format through the Moodle online submission system.

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70 views2 pages

Chem 153 Problem Set 1

This document contains instructions for Problem Set 1 assigned by Professor Yuki Oyama for Chemistry 153. Students are to [1] solve problems related to isovalent hybridization and molecular charge distribution, and [2] explain observations related to resonance. The problem set is due by March 6th in PDF format through the Moodle online submission system.

Uploaded by

wanglixiang
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Problem Set 1

Instructor: Yuki Oyama


Chem 153
February 20, 2024

Instructions: Please ensure your answers are written clearly. Submit your homework in PDF format
through Moodle by March 6th.

1 Isovalent Hybridization
(a) In bicyclo[1.1.0]butane, the J13 C−H for the bridgehead C—H groups is 202 Hz. Calculate the %s
character in the bond from carbon to hydrogen at this position. Would you expect the acidity of
the bridgehead protons to be greater or less than that of the protons in acetylene?

H
H

bicyclo[1.1.0]butane

(b) Consider the formula


J13 C−H = 5.7 × (%s) − 18.4. (1)
Determine whether this formula is equivalent to that in equation
500
J13 C−H = (2)
1 + λ2a

and explain your reasoning.


(c) Muller and Pritchard (J. Chem. Phys. 1959, 31, 1471–1476) determined that the lengths of C—H
bonds correlate with values of J13 C−H according to the equation below:

rC−H = 1.1597 − 4.17 × 10−4 × J13 C−H (3)

Use equations 2 and 3 to relate the length of a C—H bond directly to λ2a .
(d) Use your results from (a)–(c) to calculate the bridgehead C—H bond length in bicyclo[1.1.0]butane.

2 Molecular Charge Distribution


(a) Rationalize the differences between the following dipole moments for water, dimethyl ether, and
ethylene oxide (oxirane):

O O O
H H H 3C CH3
1.85 1.30 1.89

(b) Assuming that the difference in electronegativity between carbon and hydrogen is significant, de-
scribe the quadrupole moment in cyclohexane. Compare and contrast this quadrupole moment
with that of benzene.

1
(c) Ligand substitution is a crucial elementary reaction in organometallic chemistry. Consider the
following ligand substitution reactions (here Ln stands for n ligands):

H 2O
[LnNi] PPh3 [LnNi] OH2

H 2O
[LnPd] PPh3 [LnPd] OH2

It is expected that the equilibrium constant for Ni will be greater than that for Pd. Provide an
explanation.

3 Resonance
(a) Suggest an explanation for the following observations:
(i) Although the hydrocarbon calicene has so far defied synthesis, but it has been estimated that
it would have a dipole moment as large as 5.6 D.

calicene

(ii) The measured dipole moment of 4-nitroaniline (6.2 D) is larger than the value calculated using
standard group dipoles (5.2 D).

H 2N NO2

4-nitroaniline

(iii) The dipole moments of furan and pyrrole are in opposite directions.

O N
H
furan pyrrole

(b) Cyclic amines such as piperidine and its derivatives show substantial differences in the properties of
the axial C(2) and C(6) bonds. The axial C—H bonds are weaker than the equatorial C—H bonds,
as indicated by a shifted C—H stretching frequency in the IR spectrum. The axial hydrogens also
appear at higher field in 1 H-NMR spectra. Axial C(2) and C(6) methyl groups lower the ionization
potential of the unshared pair of electrons on nitrogen more than equatorial C(2) and C(6) methyl
groups. Discuss the structural basis of these effects.

N N
H H

H CH3

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