Molecular structure and chemical shifts

NMR spectroscopy

Local diamagnetic shielding

Associated with the circulation of electrons caused by the applied magnetic field around the proton itself Electron density.. Electronegativity of the group attached

Electronegativity Dependence of Chemical Shift

Dependence of the Chemical Shift of CH3X on the Element X
Compound CH3X Element X Electronegativity of X Chemical shift CH3F F 4.0 4.26 CH3OH O 3.5 3.40 CH3Cl Cl 3.1 3.05 CH3Br Br 2.8 2.68 CH3I I 2.5 2.16 2.1 0.23 CH4 (CH3)4Si H 1.8 0 Si

most deshielded

TMS deshielding increases with the electronegativity of atom X

Substitution Effects on Chemical Shift

most deshielded

CHCl3 CH2Cl2 CH3Cl 7.27 5.30 3.05 ppm

The effect increases with greater numbers of electronegative atoms.

most deshielded

-CH2-Br 3.30

-CH2-CH2Br 1.69

-CH2-CH2CH2Br 1.25 ppm

The effect decreases with incresing distance.

Magnetic ANISOTROPIC Effect

DUE TO THE PRESENCE OF PI BONDS

A proton may experience additional shielding or deshielding Magnetic anisotropic effects operate through the space no matter the influenced group is attached to the anisotropic group or not
The presence of a nearby pi bond or pi system greatly affects the chemical shift.

ANISOTROPIC FIELD FOR AN ALKYNE

H C C H
Bo
Shielded

fields subtract

hydrogens are shielded

secondary magnetic (anisotropic) field

Acetylene Protons, H2.5

 If oriented perpendicular to AMF the electrons are not free circulate and cause deshielding Net effect average over all possible orientations is affected by these aligned molecules Chemical shift observed is sum of local diamagnetic and magnetic anisotropic effects

Shielding of acetylene protons

ANISOTROPIC FIELD IN AN ALKENE

protons are deshielded
Deshielded

fields add

H C=C H

H H

shifted downfield

Bo

secondary magnetic (anisotropic) field lines

Vinyl Protons, H5-H6

Aldehyde Proton, H9-H10

Aromatic Protons, H7-H8

Ring Current in Benzene

Circulating T electrons Deshielded

Bo

Secondary magnetic field generated by circulating T electrons deshields aromatic protons

Ring current
Ring current in aromatic compounds has greater deshielding influence as compared to conjugated alkenes In Toluene methyl protons resonate at 2.34 whereas methyl group attached to acyclic conjugated alkene appears at 1.95 acetophenone

Toluene at Higher Field

Splitting patterns in aromatic groups can be confusing A monosubstituted aromatic ring can appear as an apparent singlet or a complex pattern of peaks

Terms Used
Diamagnetic Field:
an induce magnetic field against AMF

Paramagnetic Field:
an induced magnetic field along AMF

Diamagnetic shielding:
Local shielding or deshielding

Paramagnetic Shielding:
shielding or deshielding due to neighboring group

Terms Used
Diamagnetic Shift:
Downfield shift of absorption signal

Paramagnetic shift:
Up field shift of absorption signal

A Simplified 60 MHz NMR Spectrometer

RF (60 MHz) Oscillator Transmitter
hR absorption signal

RF Detector Receiver

Recorder

MAGNET

MAGNET

~ 1.41 Tesla (+/-) a few ppm

Probe

Sample Handling
0.5 ml of approximately 5% solution of the sample in a suitable solvent A few percent of the reference A liquid sample is used without a solvent if it is not viscous Ideal solvent: no viscous, inexpensive capable of dissolving the sample, chemically inert and devoid od protons of its own

Sample handling
commonly used solvents
Carbon tetrachloride, carbon disulfide, deuterium oxide, deuterated chloroform and deuterated benzene

occasionally used
CD3CN, (CD3)2SO, CD3COCD3 It is advisable to quote the solvent used