WS: Class Test 1 2016

Part A:
1.
a. Draw the two most likely isomeric forms for the complex [Pt(H)
(Cl)(PPh3)2] and briefly comment on the symmetry of the metal
complexes (5 marks)
b. For both isomers in part (a), preduct the appearance of the
following spectra:
i. The 31P {1H} NMR spectrum
ii. The 195Pt NMR spectrum [assuming J(195Pt, 31P) > J(195Pt,
1
H)]. (15 marks)
[Data: 195Pt, I = 1/2 , 33.8%; 31P, I = 1/2 , 100%].
Part B:
1. Compound A is a chiral cyclopropane derivative.
H3 C

F3 C

H
OMe
O

a. Label
compound A showing
the different
proton environments,
and the expected multiplicity of each environment.
b. State the cis and trans H-H dihedral angles between the protons
directly attached to the cyclopropane ring. Use an appropriate
diagram to illustrate one of these H-H torsion angles, using your
labels from part (a).

c.

Coupling constant

30

60

90

120

150

180

Torsion Angle

Sketch a graph showing the relationship between dihedral angle

and coupling constant (the Karplus relationship), add values to
the y-axis. (3 marks)
d. Predict the values of the coupling constants between the protons
on the cyclopropane ring. Write out these values using the
correct format (3Ja,b) using your labels from part (a).
e. Draw coupling trees for each proton on the cyclopropane ring.
f. Predict and sketch the proton NMR spectrum of compound A.
2.
The diagram below shows the protons in a terminal alkene:
Hb
CH3
H3 C
Ha

Hc
CH3
RCH3

a. Annotate the diagram below to show the expected coupling

constants between protons in the system. (2 marks)
b. Use a coupling tree to predict the appearance of the signal
for Ha
When heated, ether B undergoes a Claisen rearrangement to form phenol
C,
c. Draw the protons on both B and C and label the proton
environments in each.

H2 C
O

*
CH3

CH3

d. Which compound does this spectrum belong to? State one aspect
that supports this.
e. Which proton gives rise to the signal at 6.01ppm in the spectrum
above?
f. State the multiplicity of the signal at 6.01 ppm. Compare your
answer to that given in part b, comment on any differences. [The paper
says 5.85ppm, but this is crossed out and replaced with 6.01ppm?]
g. Draw compound C and label the carbon environments.
h. What information is shown on a DEPT90 spectrum?
i) Predict and sketch the DEPT90 spectrum for compound C.
ii) Compound C contains a stereogenic centre (marked with an
*). How can NMR be used to determine the ratio of enantiomers of
compound C produced in this reaction?
WS Class Test 2 2016
Part A
1. The crystalline compound (NH4)2SbCl5 consists of tetrahedral NH4+
cations and square pyramidal SbCl52- anions.
a. Using an appropriate character table, derive a qualitative
molecular orbital energy level diagram for the NH4+ cation. (15
marks)

b. Use group theory to demonstrate that hybridisation of the 5s,

5p and 4 d x y orbitals on antimony would be suitable for the
bond formation in SbCl52- anion. (10 marks)
c. Because of the difference in masses of the atoms in the NH4+
and SbCl52- ions, it is found that vibrations originating from the
two differentions are well separated in the IR and Raman
spectra. Use group theory to determine how many bands you
would expect to see from the SbCl52- anion in the IR and
Raman spectrum of (NH4)2SbCl5. (15 marks)
2

Part B:
2.
a. Complete the following table indicating whether or not each of
the species exhibits said spectra:
Pure Rotn

Rotn
Raman

Vib Raman

Vib IR

SF6
S2
SO

For acetylene, H-CC-H, five different vibrational bands are observed, appearing
in the IR and Raman spectra as listed in the table below:
v/cm-1
3374
3287
1973
729
612

i)
ii)

Mode

IR Spectrum
Very strong; PR bands
seen
Very strong; PQR bands
seen
-

Raman Spectrum
Strong
Very strong
Weak

Based on the data in the table, explain how this shows that the
molecule is linear.
Calculate the total number of vibrational modes for the acetylene
molecule, explain why the number calculated is larger than 5
(the number bands at different frequencies listed for the IR and
raman spectra above).
v/cm-1
Reasoning

CH stretching

CC stretching

CH bending