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Chapter 9 Nuclear Magnetic Resonance and Mass Spectrometry: Tools For Structure Determination

This document discusses two spectroscopic methods for determining molecular structures: nuclear magnetic resonance (NMR) spectrometry and mass spectrometry (MS). NMR involves placing molecules in a strong magnetic field and observing their absorption of radiofrequency energy. MS probes molecular structure by bombarding molecules with high-energy electrons. The document focuses on NMR, explaining that nuclei with odd atomic numbers or masses, like 1H and 13C, behave like tiny bar magnets in a magnetic field. It describes how NMR spectrometers work, the origin of the signal, chemical shifts, splitting patterns that reveal molecular connectivity, and how NMR can provide information about molecular structure and dynamics.

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104 views

Chapter 9 Nuclear Magnetic Resonance and Mass Spectrometry: Tools For Structure Determination

This document discusses two spectroscopic methods for determining molecular structures: nuclear magnetic resonance (NMR) spectrometry and mass spectrometry (MS). NMR involves placing molecules in a strong magnetic field and observing their absorption of radiofrequency energy. MS probes molecular structure by bombarding molecules with high-energy electrons. The document focuses on NMR, explaining that nuclei with odd atomic numbers or masses, like 1H and 13C, behave like tiny bar magnets in a magnetic field. It describes how NMR spectrometers work, the origin of the signal, chemical shifts, splitting patterns that reveal molecular connectivity, and how NMR can provide information about molecular structure and dynamics.

Uploaded by

Biopharma
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Chapter 9 Nuclear

Magnetic Resonance and


Mass Spectrometry: Tools
for Structure Determination

ORGANIC CHEMISTRY

Chapter 9

9.1 Introduction

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

How are molecular structures determined? One


way is though the use of spectroscopic methods.
Spectroscopy is the study of the interaction of
energy with matter.
When energy is applied to matter it can be
absorbed, emitted, cause a chemical change, or
be transmitted.
Nuclear magnetic resonance (NMR) spectrometry
energy absorption by molecules that have been
placed in a strong magnetic field.
Mass spectrometry (MS) molecular structure
probed by bombarding molecules with a beam of
high energy electrons.
Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

9.2 The Electromagnetic Spectrum

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

Electromagnetic radiation is one type of energy.


hc
E = hv =

NMR involves absorption of energy in the


radiofrequency range.

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

9.3 Nuclear Magnetic Resonance

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

Nuclei with an odd mass or odd atomic number have


"nuclear spin" (in a similar fashion to the spin of
electrons). This includes 1H and 13C (but not 12C).
The nuclei of protons (1H) and carbon-13 (13C), and
certain other elements and isotopes, behave as if they
were tiny bar magnets
When placed in a magnetic field and irradiated with
radio frequency energy, these nuclei absorb energy at
frequencies based on their chemical environments
NMR spectrometers are used to measure these
absorptions

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

9.3A Sweep (CW) NMR Spectrometers


NMR spectrometers can be designed so that irradiate the compound
with electromagnetic energy of a constant frequency while the
magnetic field strength is varied ()or swept().

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

9.3B Fourier Transform (FT) NMR


Spetrometers
The sample is placed in a constant (and usually
very strong) magnetic field
The sample is irradiated with a short pulse of
radio frequency energy that excites nuclei in
different environments all at once
The resulting signal contains information about
all of the absorbing nuclei at once
This signal is converted to a spectrum by a
Fourier transformation
FT NMR allows signal-averaging, which leads to
enhancement of real spectral signals versus noise
Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

9.3C Chemical Shift(). Peak


Position in an NMR Spectrum
The frequency of a signal is known as its
chemical shift.
The chemical shift in absolute terms is defined
by the frequency of the resonance expressed
with reference to a standard compound which is
defined to be at 0 ppm. The scale is made more
manageable by expressing it in parts per million
(ppm) and is indepedent of the spectrometer
frequency
Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

frequency of signal frequency of reference

10 -6

spectrometer frequency

10

Unshield

Shield

Downfield

Upfield

5
ppm

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

The spectrum is measured on a delta () scale in units of ppm


Lower frequency is to the left in the spectrum; these absorptions
are said to be downfield
Higher frequency is to the right in the spectrum: these absorptions
are said to be upfield
The number of signals in the spectrum corresponds to the number
of unique sets of protons
Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

9.3D Integration of Peak Areas. The


Integral Curve ()

The area under each signal corresponds to the relative


number of hydrogen atoms in each unique environment
within a molecule
Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

The height of each step in the integral curve is


proportional to the area of the signal underneath the
step

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

9.3E Signal Splitting


The signal from a given proton will be split by the
effect of magnetic fields associated with protons on
adjacent carbons
Characteristic peak patterns result from signal splitting
that are related to the number of protons on adjacent
carbons

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

9.4 Nuclear Spin: The Origin of the


Signal

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

Since a nucleus is a charged particle in motion, it


will develop a magnetic field. 1H and 13C have
nuclear spins of 1/2 and so they behave in a
similar fashion to a simple, tiny bar magnet.

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

E2'
E2

E = 0

E'

E1
H0
Increasing magnetic field

rh
E =
2 H0

E1'
H0'

rh
hv =
2 H0

r
r -- magnatoggric ratio
v
=
H
0
for H, r = 26750
2
v = 700 MHz, H0 = 164407 Gs
Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

9.5 Shielding and Deshielding of Protons

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

The electrons around the proton create a


magnetic field that opposes the applied field.
Since this reduces the field experienced at the
nucleus, the electrons are said to shield the
proton.

Compound
/ ppm

CH4

CH3Cl

CH2Cl2

CHCl3

0.23

3.05

5.30

7.27

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

Magnetic Anisotropy ()

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

9.6 The Chemical Shift

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

9.7 Chemical Shift Equivalent and


Nonequivalent Protons

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

9.7A Homotopic Hydrogen Atoms


()
a

H
C C

aH

CH3

CH3

C C
b

CH2Cl
CH3

Cl
C C

+
H

CH3
CH3

Chemically equivalent or homotopic

Homotopic atoms ( or groups) are chemical shift


equivalent
Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

9.7B Enantiotopic() and


Diastereotopic () Hydrogen Atoms
If replacement of each of two hydrogen atom by the same group
yields compounds that are enantiomers, the two hydrogen atoms are
said to be enantiotopic.
Enantiotopic hydrogen atoms have the same chemical shift and give
only one 1H NMR signal.

Br
H

H
CH3

Br
H

Br
Z

CH3

H
CH3

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

If replacement of each of two hydrogen atoms by a


group, Z, gives compounds that are diastereomers, the
two hydrogens are said to be diastereotopic.
Diastereotopic protons do not have the same chemical
shift and give rise to different 1H NMR signals.

Cl

H
C C

H
H
CH3

Cl

H
C C

C C
H

Cl

OH CH3
C
C
H

Diastereotopic protons
Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

9.8 Signal Splitting: Spin-Spin Couping

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

Coupling constant

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

Department of Chemistry, Xiamen University

ORGANIC CHEMISTRY

Chapter 9

9.9 Proton NMR Spectra and Rate


Processes

Department of Chemistry, Xiamen University

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