Documente Academic
Documente Profesional
Documente Cultură
0 = 0 = I ( I + 1) =
Nuclei of interest 1H, 2H, 13C, 19F, 29Si, 31P, 127I, etc.
Any nucleus with an odd Z or an odd A has a net spin. magnetogyric ratio of the nucleus
http://www.chem.queensu.ca/FACILITIES/NMR/nmr/webcourse/index.htm
Nuclear angular momentum of 0 0 = I ( I + 1) = http://www.eclipse.net/~numare/nsinmrpt.htm
# orientations (states) in a B =2I+1 Precessional cone
Each state characterized by mI = -I, -I+1,.+I Of a single
Z, B0
nucleus 0 0, dipole
moment
I = 1/2
mI = +1/2; , ground state m = m I =
m
mI= -1/2 0 = B0 Vertical component
remains steady.
B 54.7o
Horizontal component
Energy
Y
changes direction.
mI = +1
mI = + , low energy
I=1/2 mI= 0
I=1
mI = - 1/2
http://www.bruker-nmr.de/guide/eNMR/chem/NMRnuclei.html mI= -1
mI=+3/2
Transitions
I=3/2
between states
Selection rule: dictated by
mI=1 selection rules
or
mI= - 3/2
Energy Changes in a varying B
1
1 E = [+ =]B
+ z = + = 2
2 m= -1/2, state
E anti-parallel to field,
B
1
E = [ =]B
1 0,0 2
z = = 1
2 E = [ =]B B
2 B0
m= +1/2, state
E = =B B , parallel to field,
1
E = [+ =]B
2
magnetogyric ratio of the nucleus z = mI = Z
E = B
E = =B0 = h
falls in the radio frequency region.
E = =B0 = h 0
E B0
0 =
0,0 2
B
0
B0
B
B E = =B0 = h 0
B
B0
Continuous wave experiment; Frequency sweep Proton in a sample are in a different electronic environment
B constant than a bare proton. Protons with different type of environments,
characterized by , can be recognized.
High
(1 ) B0 Therefore of absorption
= of each type of H is unique.
2
E
N
The pseudo NMR experiment is impractical, i.e. absorbance =e kT
cannot be measured directly by experiment. N
The reason for it is a population distribution issue and the N E E
nature of the interaction of electromagnetic radiation with = 1 Using Taylor series for << 1
matter (energy levels of matter).
N kT kT
N E
very small N N E
Boltzmann Law
=e
kT =
N N kT
E
N N = N
For protons = 26.75 107 rad/T s; h-bar = 1.055 10-34 Js, kT
k = 1.380658 10-23 J/K. At 298K and B0 = 7.05T
Population excess is linear in E
N under this condition.
= 0.99995 1 N N
N
Samples contain millions of molecules. All nuclei of the same Relationship between energy levels,
type would precess at the same Larmor frequency. magnetic field and shielding:
The vector sum of the magnetic moments of one type of nuclei is Low , low shielding
a measure of the number of protons of that type in the molecule. High transition energy
O Same B
Ma:Mb:Mc=3:2:3
H3C
CH3
(1 ) (1 )
a b c = B0 slope = 2 =
2 2
Chemical Shift raised _
(1 ) B0
=
2 B0
0 =
2
Further it should give a single sharp nmr signal. The most common reference compound used is
tetramethyl silane. TMS is rich in Hs(12) and methyl group Hs
It should be chemically un-reactive and easily removable from are richer in electrons (larger ) than in many organic compounds
the sample after the measurement. and they are structurally equivalent.
ref =H(1-ref)B0
6 6
89.999510 89.999010
6
For bare 1H(=0)at 2T field resonate at 90.0000 MHz; Chemical Shift (ppm): 10 = 5.556
6
90 10
A typical proton would have a frequency of 89.9995 MHz,
it is an unwieldy number to report, further if a different
Frequency shift (Hz) 6 6
instrument (different field) is used the frequency will be 89.9995 10 89.9990 10 = 500
different.
Frequency shift in a 300MHz instrument (Hz):
Thus absorption positions are reported with respect to a 6
( 5.556) 300 10
reference. If a reference compound resonates at 89.9990MHz. = 1666.8
6
10
6 6
Chemical shift:
89.999510 89.999010
6 Entire proton range 300MHz instrument is 12ppm.
10 = 5.556
6
90 10
In (Hz): 6
( 12) 300 10
= 3600
6
10
Chemical shift decreases with increasing shielding of the nucleus The higher the field the larger the frequency range over which
the spectrum spreads. This enhances the resolution of peaks.
Low , low shielding
High transition energy
Same B
( ref )
ref = B
2
Frequency shift is dependent of the instrument field strength. The resonance frequencies of nuclei in similar environments
are the same.
Most of the time the NMR spectrum consists of groupings of The chemical shifts of protons in a molecule can differ in
multiple lines (multiplets). This is due to 1H - 1H coupling (spin- various degrees.
spin splitting/J-coupling/scalar coupling). The nuclei which are
1 to 3 bonds away (especially) would feel the nuclear spin Depending on the extent of coupling (J) between the
state of each other via the electron spins of the intervening nuclei, the splitting pattern changes.
bonds. That generates the splitting of spectral lines.
Simple rules (n+1) and area ratios (Pascal triangle) is useful for
H Br H H weakly coupled systems (first order spectra).
| | | |
Cl C C Br Cl C C Br The spin system, in general, for example is referred to as AnBm
Geminal 2J | | | | Vicinal 3J (second order spectra) if the chemical shifts are quite close
H Cl Cl Br together, and AnXm (first order spectra) if the chemical shifts
are far apart relative to J.
Only magnetically nonequivalent nucleii couple.
Pople Notation
CH3 H CH
H3C 3 A6X
Each chemically different type of proton is given a capital letter; A3X2
A,B C M,N. X,Y,Z.
The number of protons in a group protons is indicated as a
subscript; A2, B3
Protons with similar values are assigned letters close to one
another in the alphabet; A,B,C; M,N; X,Y, Z. H
H3C OH A3X2
H AMX
Two protons same chemical shift but magnetically nonequivalent
is assigned, for example AA. H3C O H
+
N A3M2X2
AX, AM weakly coupled, AB strongly coupled pair of protons. O
-
Three protons very different in from each other (and therefore H3C
I A3B2X2
weakly coupled) would be like AMX, ABX, BX weakly coupled,
AB strongly coupled.
First-order Scalar Coupling (weakly coupled systems) Consider an AX system:
Coupling of spins lead to peak splitting (hyperfine structure). A molecule which contains a proton (HA) attached to a C, and
In first order spectra the splitting of the peaks follows a simple that this C is attached to another C carrying a proton (HX). In
pattern. this situation HA feels the presence of HX via bonding
H3C A6X electrons.
A H3C CH3
O
O
Protons are tiny little magnets, that orients either parallel or
anti-parallel the magnetic field B0 of the instrument. When the
field created by HX effectively reinforces the magnetic field B0
HA feels a slightly stronger field, but when the field created by
HX opposes B0, HA feels a slightly weaker field.
13C-1H AX System 1J
(1 ) B0 HX HA
= | | Fermi contact Pauli Principle
2
Cl C C Br
| |
Cl Br
>8 High energy
J
A A X
X
Isolated atoms Fermi
contact energetically favors Low energy
anti-parallel orientation
of spins. Bonded atoms Pauli Principle
B0+BA B0-BA B0+BX B0-BX
demands anti-parallel electron
spins making nuclear and
3J 3J electron spins parallel, .
XA HX AX HA
13C-1H AX System 1J 13C-1H AX System 1J
C
The difference in
the nuclear spin of
bonded atom (left) gave
rise to four eigen states.
If otherwise it
would be two eigen
states and one frequency. C
Eigen-states with no coupling Effect on eigen-states with coupling
H H
13C-1H AX System 1J AX System 3J
Cl Br
Cl Br
J/4
+ (J/4/ + J/4)
Fermi contact
C
J/4 J
A X
C C
Pauli Principle
J/4
- (J/4/ + J/4)
C
J/4 Hunds Rule
For the X peaks a similar situation (doublet) would form. High energy
H H
Cl Br
AX System 3J
Fermi contact Cl Br
J/4
+ (J/4/ + J/4)
A X
X
J/4
Pauli Principle
H H AX System 2J AX System 1J
C
J/4
- (J/4/ + J/4)
X J/4
A A
X X
Regardless of sign J
the splitting pattern
would be the same for
J/4 same value of J.
High energy Low energy !!
+ (J/4/ + J/4)
X
J/4
J<0
Stick Diagram first order splitting due to scalar coupling Stick Diagram first order splitting
A
Spin System # Peaks
(n+1)
AX 2
J
AX2
Splitting pattern of the first order spectra are extremely useful Instruments with larger fields simplify the second order
To extract information about the connectivity and the pattern to a first order pattern.
stereochemistry of the molecule.
The magnetic moments for each type of nuclei are moved onto
the x-y plane.
Note: Methylene protons
are magnetically non-equivalent.
The FID collected.
Each H 1:3:3:1 pattern &
are overlapped.
Caution: Overlapped peaks ratio
not Binomial coefficients!!. -CH2-
Z
Collection of nuclear
dipole magnetic
moments - symmetrical
components
Magnetic moment
vector, single B0
B0 nucleus
Z
Z Z
Net vector of nuclear
dipole magnetic Tilt angle
moments, M0. M0
x
M0
B0 Y
X
X
Transceiver
Y
Use the Right Hand Rule.
X X X X
Y
t=0 T/4 T/2 3T/4 ..
X
Induced Voltage receiver mode
1D-H-NMR Experiment: One Pulse Experiment (Single Channel) Fourier Transformation of FID
Place the sample in the magnetic field. The signal detected is a time domain signal. The signal
The nuclei attains equilibrium composition. Net magnetic moments decays due to the T2 relaxation and is therefore called free
orient on z-axis. induction decay (FID). The equilibrium magnetization is
After a recycle delay, d1, apply a RF pulse (=/2). directed along the external magnetic field in Z). The time-
The magnetic moments for each type of nuclei are moved onto dependent signal can be converted into the frequency
the x-y plane. domain by the Fourier transformation
The FID collected (detector response).
=/2
Collect and add many FIDs.
d1 AQ d1
H H
Cl Br
AX System 3J
Cl Br