Fluorine and Phosphorus NMR
Fluorine Nuclei properties
• 19F -100 % natural abundance
• Magnetogyric ratio: about 0.94 times of 1H.
• A range of > 350 ppm for organofluorine
compounds.
Effect of Number of F
Effect of various substituents
Spatial steric influences
Chemical Shift Range
FMR and PMR of 1,1,1-trifluoropropane
Coupling constants F-H
F-H coupling constants
Coupling constants
Effect of chemical environment
Fluorine - Fluorine Coupling
C-F coupling constants
Second Order Spectra
Secondary effect
F-decoupled spectra
FMR and PMR of CF2=CH2
PMR and CMR shift of F compound
Gem coupling of Fluorine
NMR of gem-difluorocyclohexane: variation
with Temperature
Proton NMR spectra of Fluorinated
compounds
Proton NMR spectrum of difluroalkane
Carbon NMR of difluoro compounds
Carbon NMR of difluoro compounds
Change in Fluorine chemical shift
depending on substituents
Fluorine NMR spectra of Difluorocompounds
with different chemical environment
PMR of 1,1-Difluorobutene
13C NMR spectra
Chemical shift and coupling constant values
Carbon and proton NMR of different
fluorinated compounds
Carbon and proton NMR of different
fluorinated compounds
Carbon and proton NMR of different
fluorinated compounds
Natural Abundance
• 31
P (100%), 19F (100%), 11B (80.42%),
• 27
Al (100%), 29Si (4.70%), and 195Pt (33.8%)
Chemical shifts of Phosphorus and chemical
environment
Substituent Effect
Substituent effect
Electron withdrawing substituents
1
JPH Coupling Constants
• The value for 1JPH increases with decreasing electron density on
phosphorus.
• Inthe series PH4+, PH3, and PH2-, the 1JPH coupling constants are 547
Hz, 189 Hz,and 139 Hz, respectively.
• It appears that the influence of electron lone pairs on the 1JPH coupling
constant becomes smaller with each lone pair.
• JPH for PH4+/PH3 is 358 Hz, whereas for PH3/PH2- is only 50 Hz
1
• PH3, which has a 1JPH coupling constant of 189 Hz as a free ligand,
but a significantly larger one in its complexes: 307 Hz in
[Cr(CO)4(PBu3)(PH3)], and 366 Hz in Me3BPH3, respectively.
Internal Standard
• Methylphosphonic acid (MPA)
• Used to determine the phosphorus content of carbonated
beverages, MPA is a reliable and simple internal standard for
quantitative 31P-NMR analysis.
• Triphenyl phosphate and sodium phosphate
• These are phosphorus-containing references that can be used
as internal standards for different applications and solubilities.
• Potassium dihydrogen phosphate (PDP) and phosphonoacetic
acid (PA)
• These are water-soluble 31P-qNMR standards that can be used
for quantifications based on NMR.
• Hexamethylphosphoramide (HMPA)
• This can be used as an internal standard in quantitative 1H-
NMR methods for determining ribose content.
