Professional Documents
Culture Documents
Physical Methods in Inorganic Chemistry Magnetic Resonance: Lecture Course Outline Lecture 1: A Quick Reminder
Physical Methods in Inorganic Chemistry Magnetic Resonance: Lecture Course Outline Lecture 1: A Quick Reminder
Magnetic Resonance
Physical Methods Magnetic Resonance
A quick reminder
A few trends in Inorganic NMR
A little more on Chemical Exchange
Essential NMR Methods
Spin Decoupling
Spin Relaxation Measurements (again and more)
Lecture 2:
Lecture 3:
Magnetic
Resonance
Gyromagnetic ratio
(107 rad T-1s-1)
26.75
8.58
6.72
1.93
-2.71
29.18
6.98
-5.31
10.84
7.05
6.35
5.12
-0.85
-1.25
-10.02
6.43
-8.50
1.12
0.50
5.80
4.82
E / cm-1
Co(PF3)3-
-4200
Co(CN)63-
26300
Co(NH3)63+
6940
23210
Co(en)33+
7010
21400
Co(NO2)63-
7350
20670
Co(acac)3
12300
16900
p|*
Chemical Exchange
Remember:
( A B )
k
2
Examples of Fluxional inorganic systems.
Axial-equatorial exchange in trigonal bipyramidal systems
(PF5, SF4, PF4NMe2 , Fe(CO)5)
Bridging/axial exchange in carbonyls.
Bridging terminal exchange in boranes (B2H6 etc.);borohydrides (Al(BH4)3)
Ring-whizzing in 1-cyclopentadienides (Cu(PMe3)( 1-C5H5)
Interchange of ring bonding modes in compounds with mixed heptacity
( e.g. (1-C5H5)2(5C5H5)2Ti: (4-C6H6)(6-C5H5)Os
17
O spectrum of Co4(CO)12
Fa
Fe P
Fa
N(Me)2
Fe
19
13
Recall: multiplets
2nI + 1
I(6Li) = 1
Jav = (5.4 Hz 3 + 0)/4
= 4.1 Hz
x
J(13C-6Li) = 5.4 Hz
n=4
n=3
NMR Acronyms
Nuclear
Overhauser
Spectroscopy
Correlated
Spectroscopy
Electron Nuclear
Double
Resonance
Magic Angle
Spinning
Methods
Continuous wave
E
h
B
z
y
y
x
z
y
y
x
NMR Signal
I()
M z ( ) M 0 ( 1 2e
T1
echo
y
x
x
y
y
x
s
m
f x
2
T2
Echo Trains
A
A
X( )
irrad at X
X( )
A( )
A( )
Notation: A{X}
A
Irradiation of X at its
resonance frequency
induces rapid transitions
from X( ) to X( ) and vice
versa. A sees a single,
averaged field.
B2 of same order as 2JAX
X should be sufficiently far
away from A
ii) irrad
Fa
Fe A
Fa
X
X
i) irrad
I(A) = I(X) = 0
ii) irrad
i)
Fe{Fa}
ii)
Fa{Fe}
31
31
P(CH3CH2O)3
irrad
P(CH3CH2O)3
31
I( P)=1/2
31
P(CH3CH2O)3
irrad
31
P(CH3CH2O)3
Recall: Exercise
B = 1.41T
Electron:
H:
N lower
N upper
g B B
1
0.904
kT
N lower
B
1
0.999855
N upper
kT
Can we
transfer this
polarisation?
0
13
sat
3
4
2
sat
13
5
Boltzmann
3
Protons saturated
4
Cross Relaxation
Takes spins from top to bottom
level, competition with 13C
relaxation (restoring Boltzmann
in 13C population)
intensity)
maxI/S
where I is the saturated spin and S is the observed spin.
Maximum effect occurs when there is no leakage as a
result of relaxation mechanisms other than the dipoledipole interaction (a through space interaction!).
For homonuclear systems, maximum enhancement is 50%.
Remember that 15N and 29Si have negative .
irrad
Difference Spectrum
Integration
29
SiH(Ph)3
29
Proton Decoupled
Coupled
Magnitude:maxI/S
~ -1.5
FT
A 2-Dimensional Experiment
evolution
t1
evolution
t1
evolution
t1
Series of onedimensional
NMR spectra
must be
recorded
Amplitude Modulation
t1
t1
Phase Modulation
t1
t2
Pulse Sequence
z
t1
x
y
y
x
Pulse
Sequence:
t1
y
x
t2
y
x
t1
t2
=
y
x
F1
Pulse Sequence
Aim : To discover spin-spin
couplings in a molecule.
Answer: Which resonance
belongs to which nucleus?
t1
t2
1
1
J ( A, X ) A2 : A J ( A, X )
2
2
1
1
X 1 : X J ( A, X ) X 2 : X J ( A , X )
2
2
A1 : A
2
3=4
1=2
5=6=7=8
9=10
a
d
b
c
S
S
xx
x x x
t1t1
mm
tt22
S
S
2D NOESY vs 1D NMR
2 D NOESY Why?
Advantages wrt 1D 1H{1H} NOE:
Simplification of crowded spectra
No need for selective excitation of individual
resonances
Higher efficiency
NMR in Solids
Physical Methods Magnetic Resonance
Problems:
Through Space dipolar coupling not averaged out
Distance dependent information on spin
(broadened spectra)
separations!
repulsion
attraction
Bz
Bx
y
x
0
Bx
3 sin cos
3
4 r
By 0
0
2
Bz
(
3
cos
1)
3
4 r
Anisotropic quantity
Recall:
for
(Ph)331PO
per
par
static
1.9kHz
3.8kHz
2Ca(CH3CO2)2.H2O
M o d u la t io n D e p t h
Electron Paramagnetic
Resonance (EPR)
=
Electron Spin
Resonance (ESR)
1
0 .9 5
0 .9
0 .8 5
0
0 .5
T im e / s
1 .5
E R samples
Paramagnetic
Most substances do not contain paramagnetic species
and are hence EPR silent
Advantage
1) Easier to interpret
2) Introduction of Spin Spies
Disadvantage
Fewer accessible systems
a)
S
N
O
b)
O
H2N
+ Protein-SH
S
S
N
Protein
OH
Applications of EPR
Physical Methods Magnetic Resonance
Applications of EPR
Study of N@C60 (and others)
Quantum Computing
Phase transition temp: 260K
4
S3/2
(14N) = 1
FT-EPR
K.P. Dinse
Local Structure
Physical Methods Magnetic Resonance
ENDOR/ESEEM in proteins
Applications of EPR
cf.
EI = - mIhB0
(nucleus)
H frequency/MHz
200
400
mS = +1/2
B0/T
10
20
mS = -1/2
Q
X
W
100
300
ESR frequency/GHz
The g-value
Physical Methods Magnetic Resonance
E = mSgeBB0
ge
In case the electron
is the only source of
magnetism in the
sample
E = mSgBB0
SO coupling (SO constant )
leads to derivation of g from that
of free electron
n
g
Ees E gs
h
(GHz )
g
0.07145
B B
B (T )
For most organic radicals, g ge
For transition metals, large deviations from ge
possible
g can be measure to high accuracy (0.0001)
g is the chemical shift of NMR
g depends on structure of radical, excitation energies,
strengths of spin-orbit couplings
Note: later, we will discuss that g is anisotropic and not actually a scalar but a tensor.
S in field
Hyperfine Coupling
I in field
S I
I
SI
aiso/4
aiso/4
S
S
I
SI
(mS , mI ) mS S mI I mS mI aiso
mS 1, mI 0
aiso/4
SI
aiso/4
|aiso|
S
1 spin nucleus
SI
SI
Sb
Sb
2 spin nuclei
SI1I2
SI1I2
SI1I2
SI1I2
SI1I2
SI1I2
SI1I2
SI1I2
(mI ) S mI aiso
3 spin nuclei
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
SI1I2I3
2 (2 I k 1)
k
ne (2 I k 1)
k
(mI ) S mI aiso
Isotropic:
Directional:
Interactions between vectorial quantities:
scalars
vectors
tensors
g 'ij g ' ji
Diagonalise
g xxx
g yyy
g zzz
Principal values
Anisotropy:
g iso 1 ( g xx g yy g zz )
3
g g zz g iso
Asymmetry:
( g zz g xx )
Isotropic g:
g ( g sin cos
2
xx
g sin sin
2
yy
g cos )
2
zz
1/ 2
Powder
spectrum
1st derivative
g xx
g yy
g zz
g g zz
g g xx g yy
And:
g ( g sin g cos )
2
1/ 2
A Aiso Adipolar
Recall:
Fermi contact Interaction
(discussion of J)
Density of unpaired electron at
nucleus (s-orbital character in
SOMO)
ISOTROPIC
Recall:
Dipolar Interaction, D
p,d,f orbital character in
SOMO
Averages out in solution
ANISOTROPIC
A Model Cu system
2+
Axial symmetry
Li ( CO2 )
+ 13
12
How?
A strong radiofrequency (NMR) field induces NMR
transitions which are observed as a change in the intensity
of an electron resonance condition.
Electron Nuclear Double Resonance (ENDOR)
Recall:
S I
aiso/4
aiso/4
I
SI
S
S
S
SI
aiso/4
SI
aiso/4
Recall:
1
1
1
E4 s I a
2
2
4
1
1
1
E3 s I a
2
2
4
4
3
| S I
| S I
1
1
1
1
sat
1
1
1
E2 s I a
2
2
4
1
1
1
E1 s I a
2
2
4
| S I
| S I
Previous overhead
Relative populations are given by Boltzmann at thermal equilibrium
(I<<S, hence populations of 1 & 2, 3 & 4 assumed identical)
Irradiate 1-3 transition (saturate at high power) same
populations in 1&3 now
Irradiate system with RF (NMR) and sweep frequency whilst
continually saturating EPR transition; observe the intensity of its
absorption
When RF frequency matches |I-a/2|, transition 3-4 will be
induced, restoring some population difference between levels
1&3
More EPR absorption now possible this is an ENDOR signal
Equally, when RF frequency matches |I + a/2| (1-4 transition), this
time a pumping from 1-4 occurs (as 4 has the higher population)
and a population difference between 1&3 is again achieved and
EPR transition enhance the second ENDOR signal
In practice, need to consider spin lattice relaxation processes
EPR spectrum
ENDOR
Orientation Selection
EPR
Hyperfine
couplings not
resolved
1
H ENDOR
Toluene Solvent