10/09/2014

PARAMAGNETIC MATERIALS

•  Paramagnetic materials by shortening relaxation times

cause line broadening.

•  They also cause a shift in signals.

NMR •  Co and Ni cause severe line broadening thus cannot be
used.

SHIFT REAGENTS
•  Lanthanide ions are found to cause shifts without line
broadening.

SOLVENT EFFECTS

•  Nonpolar (CCl4)

•  Polar (DMSO)

•  Anisotropic (Benzene)

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SHIFT REAGENETS
MOST COMMON “LSR”

•  The shift reagents reduce the shielding of all R

R = t-butyl, Eu(dpm)3

protons.
O
Tris(dipivaloylmethanol)-Eu(III)



•  The shift increase with the proximity of the R = -CF2CF2CF3, Eu(fod)3

protons to the shift reagents.

CH
Eu

•  The OH proton may be shifted more than 20 O

ppm.

CH3
C
CH3

CH3

3

MECHANISM

Eu(DPM)3
•  Paramagnetic elements act like solvent of pyridine and benzene
and create a secondary magnetic fields which are usually
anisotorpic.







H



L + S LS R-O……Eu(DPM)3



•  Two mechanisms cause paramagnetic shifts


a. Contact interaction


b. Dipolar (pseudo-contact) interactions

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DIPOLAR INTERACTION

CONTACT INTERACTION

The contact interaction involves

The dipolar interaction (pseudocontact)

is used to describe a dipolar interaction

direct delocalization and/or spin

between the magnetic dipole field of

polarization of the unpaired electron
the unpaired electron and that of the

via the molecular orbitals of the
nucleus being observed.

substrate ligand. The contact may
This interaction is transmitted through

involve both π and σ bonds.
space and depends on the geometry of

the complex.

3cos2v-1

_________

∆Dip. = K
•  The shift decreases in inverse proportion to r3.

r3




•  The value of ∆Dip. is independent on the nuclei
r = Distance between paramagnetic ligand
being observed (1H or 13C)

L and the nucleus R being observed e.i.
•  ∆Dip. can be positive or negative, depending on
1H or 13C.

whether (3cos2v-1) is greater than or less than
zero.

r

L
v
R

O C

H

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The experimentally measured chemical shift

APPLICATIONS

is given by:




δexp. = XS(δS) + XLS(δLS)
•  Simplifying complicated spectra (Qualitative)

•  Determining accurate geometrical data for the LS
complex and hence for the molecule of interest
δS = chemical shift of free substrate
(Quantitative)

δLS = chemical shift of L-S complex

XS and XXL = molar concentrations of

substrate and complex

respectively.

•  Spectrum A is pure substrate

•  Increasing the concentration of LSR, increases the deshielding of
protons.

•  The effect is greatest for NH2 protons.

•  In spectrum D, -NH2 protons appear at 12.1 ppm.

•  o-protons of aromatic ring are effected the most.

•  In spectrum H, the signals due to shift reagents begin to appear.

•  Linear correlation is observed between LSR vs


chemical shifts.

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The magnitude of the induced shift depends on

a.  Concentration of the LSR

b. Complex forming strength of the substrate.





NH2 > OH > C=O > COOR > CN



c. Olefins and arenes do not show LSR induced


shifts since they cannot form complexes with


the lanthanide ion.

O
2 OH CH3
1
2 1 CH3 -CH-CH LSR with
2 3
3 N 1 CH 3
13C spectra

4 H
4 Enantiomers are not differentiated by NMR
spectrum. However, it is possible to convert a
A!!!!!!!!!!!!!!!!!!!!B!!!!!!!!!!!!!!!!!!!!!!!!C racemic mixture with chiral reagents into
Comp.
LSR

1
2
3
4
diastereomers.
A

Eu(dpm)3
48.9 17.2 11.5 7.5



Pr(prm)3
-65.9 -27.9 -14.9 -10.5

S(+) + L(-) S(+)L(-)
B

Eu(dpm)3 142.8 -8.2

S(-) + L(-) S(-)L(-)



Pr(prm)3 -149.5 -40.0

C

Eu(dpm)3 23.5 60.1 15.3 14.1



Pr(prm)3 -42.3 -92.1
-36.0 -23.6

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CHIRAL SHIFT REAGENTS

Tris(3-(222-trifluoro)-1-hydroxyethylidene)-d-

camphorate) Eu(III)

CHIRAL SOLVENTS

Chiral acids, amines, alcohols, sulfoxides and

Cyclic compounds can be used as chiral

Solvating agents (CSA)

(+)-2-methoxy-2-(trifluoro-

methyl)-phenylacetic acid