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Shift Reagents

but not equally for all resonances – useful in spectral analysis (✣) .Why are the shift reagents used in NMR spectroscopy?  Presence of paramagnetic impurities in the sample: • shortens the relaxation times. which causes • • line broadening () useful in integration in 13C NMR: suppresses the NOE (✣) causes a shift of the signals.

Lanthanide shift reagents (LSRs)     Paramagnetic ions of Ni and Co were the first used shift reagents a big drawback: severe line broadening On 1969 Hinckley discovered that paramagnetic lanthanide ions gave shifts without significant line broadening Example: 90 MHz 1HNMR spectrum of 1hexanol in the presence of chelate complex Eu(III)-tris(dipivaloylmethanate) .

Eu(III)-tris(dipivaloylmethanate)  remarks: • • all the protons become less shielded. all the CH2 groups become separated the shifts increase with the proximity of the protons to the OH group of alcohol .

How does this shift effect occur?   interactions between nuclear spins and the spin of the unpaired electrons of paramagnetic ions two types of interactions: • the contact interactions • the pseudocontact interactions .

Both types of interaction depend on: the formation of a complex between the substrate S and the paramagnetic metal ion L  In solution there exists a dynamic equilibrium between the free components and the complex: L+S LS Example of a complex: H  O R Eu(DPM)3 .

and β-positions relative to the complexing center (e. N or S) In conjugated systems more distant positions could be affected as well The contact term is very important in 13C NMR . O.The contact term      is based on the contact interaction: the spin density of the unpaired electron is transferred to the substrate molecule the electron spin density is not the same at all positions of the observed nuclei throughout the molecule in saturated compounds the most affected 13C nuclei are those in α.g.

The pseudocontact term    this type of interaction is of greater importance in 1H NMR then the contact term the name pseudocontact is used to describe a dipolar interaction between the magnetic dipole field of the unpaired electron and that of the observed nucleus the interaction is transmitted through space .

constant which depends on the magnetic dipol moment of the paramagnetic metal ion the equation is valid if the complex is symmetrical about the L-O axis  L r R υ O H C .Geometry of the complex the shift in the resonance frequency of the observed nuclei depends on the geometry of the complex: DDip= K(3cos2 υ -1)/r3 K.

Conclusion about 1H shifts in the presence of lanthanide reagents ∆Dip= K(3cos2 υ -1)/r3    the shift effect decreases in inverse proportion to r3 it is independent on the observed nuclides can be positive or negative (depending on the sign of (3cos2 υ -1) term) .

Applications  simplifying complicated spectra • separation of overlapping signals • easier assignment • integration of signals which are otherwise •  overlapped decoupling experiments determining accurate geometrical data for the LS complex and hence for the molecule of interest .

a solution is found: silver(I) ions • • they make complexes with π-electrons if they are added in the form of AgFOD to the solution containing the substrate and the LSR.1.they do not show lanthanide-induced shifts (do not form complexes with lanthanide ions) however.3.1. shifts are observed for olefines and arenes(CH3)3C CF2CF2CF3 O O 1.6-octandione (FOD) • obviously.)   troubles with olefinic and aromatic protons . the silver ions are able to transmit the shift effect .3-heptafluoro-7.2.7-dimethyl-4.Applications (cont.2.

it becomes possible example: mixture of 1-phenylethylamine's enantiomers LSR: the chiral complex Eu(TFC)3 .Chiral LSR      Enantiomers are indistinguishable by NMR not possible to determine if the sample is a pure enantiomer or a racemate by using a chiral reagent and making diastereoisomers or diastereomeric complexes.

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L(-)) gives the two solvation diastereomers (S(+)L(-) and S(-)L(-)) this can lead to separate resonances in the NMR spectrum .Chiral solvents     Interactions between solutes and solvents can induce shifts as well our focus: interactions between chiral compounds and chiral solvents (CSAs. chiral solvating agents) a racemate (S(+) and S(-)) dissolved in a chiral solvent (e.g.

2-trifluoro-1-phenylethanol NH2 H C CH3 1-phenylethylamine .The most common CSAs  chiral • • • • • acids amines alcohols • fluorinated sulfoxides cyclic compounds OH H C CF3 2.2.

Mixture of achiral solvent + chiral reagent + chiral substrate   A shift effects are observed very often in such mixtures example: 1H NMR spectrum of mixture of • the racemate of 1-phenylethylamine • solvent: CDCl /DMSO • (+)-2-methoxy-2-(trifluoromethyl)phenylacetic 3 acid .

COOH CH3O C CF3 (+)-2-methoxy-2-(trifluoromethyl) phenylacetic acid .

Influencing factors  The induced shifts depend on: • • • • •   the chosen solvent the substrate (analytes) the complexing strength temperature concentration ratio The effect is not observed for solvent signals reason: fast exchange of solvent molecules between complexes with both substrate enantiomers .