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2019 Chemistry 143 NMR Spectroscopy Problem Set #2 Due Friday April 19, 2019

Problem 1 When rhodium complex 1 is treated with hydrogen gas, ethylene is released and
compound 7 is formed.
(a) Identify the nuclei that would be expected to couple to the bridging hydride nuclei. Are the
hydrogen nuclei magnetically equivalent in the structure shown ?

(b) The far upfield hydride region of the 1H NMR (400 MHz) spectrum of the dimeric complex
in C6D6 (d6-benzene) is shown below with a simulated spectrum. Calculate the coupling
constants associated with this molecule.

Problem 2 For the NMR figure at right, use “coupling


trees” to describe each signal and give the J values for this
system.
Problem 3 (a) Choose the correct structure of C10H14O3 from the 1H NMR (500 MHz, CDCl3)
spectrum provided. For each of the other structures, indicate one reason why it is incorrect.
O O
O O CH3 CH3 O CH3 O
CH3
CH3 CH3 O
O O O
CH3 CH3 O CH3 CH3 CH3 CH3
O O O O O O O
(b) Explain the origin of the four proton multiplet found near 2.8 ppm and assign each
individual proton to a carefully drawn structure which you have chosen.
Problem 4 (a) A researcher brought a 400 MHz 1H
NMR spectrum of compound 1 shown below with
several questions. O
Me
O

(a) Why am I not seeing a triplet at 2.98 ppm ? Me


N2 Me
C

(b) Is the signal at 3.12-3.17 ppm (shown in the Me


expansion below) an impurity ?
1 2
Answer these two questions and use one of the
Excel spreadsheets demonstrated in class to
simulate this spectrum and derive the individual J
values for this system.
Problem 5. Propose a structure for the ester C8H12O2. 1H NMR (300 MHz, CDCl3) and 13C
NMR (75 MHz, CDCl3):

Problem 6. Grushin and coworkers have prepared an organometallic cluster by treating


Ph(PPh3)PdOH dimer with CpCr(CO)3H at room temperature (Organometallics 1997, 16, 97).

H
Ph O Ph -H2O O Cr O
Pd Pd + OC Cr
CO
C
C
C

Ph3P O PPh3 OC H Ph
Pd Pd Ph
H O O
Ph3P H PPh3

The 1H decoupled 13C (75 MHz) spectrum of this complex


shows a triplet at 243.2 ppm and a more complex pattern at
244.6 ppm (as shown below). The 1H decoupled 31P spectrum
of this molecule shows a singlet at 18.0 ppm.
(a) Draw the isotopic species responsible for the complex signal
in the 13C spectrum.
(b) If the phosphorus atoms are participating in this
phenomenon, why does the 31P spectrum only show a singlet?
(c) The simulated spectrum shown above was obtained by using
JPP = +5 Hz and 3JCP = +5 Hz. Using the ABX excel
spreadsheet calculator used in class, test these two values with
2JCP = +19 Hz and then using 2JCP = -19 Hz. What is the most
reasonable choice for Δν for this system? Which choice
reproduces the simulated spectrum from the publication?