PositionofSignals:TheChemicalShift BasicVocabulary: ChemicalShiftthepositionofasignalinanNMRspectrum. Deshielded(downfield)anucleuswhosechemicalshiftisincreased,feelsstronger magneticfieldduetotheremovalofelectrondensity,magneticinduction,etcin neighboringatomsorgroups IntegrationInNMRspectroscopy,theprocessofmeasuringtheareaofanNMR signal.Itisusedtodeterminetherelativenumberofhydrogensthatcorrespondto eachsignal. MagneticInductionInNMRspectroscopy,thephenomenonthatanexternal magneticfieldcausespielectronsinanelectroncloudtocirculate.Asthese electronsmovearound,theirownelectricchargecausesthemtocreatetheirown magneticfield. PpmInNMRspectroscopy,thexaxisunitsofthechemicalshiftscale.Theppm scaleincreasesfromrighttoleft.

ft. Shielded(upfield)anucleuswhosechemicalshiftisdecreased,feelsweaker magneticfieldduetotheadditionofelectrondensity,magneticinduction,etcin neighboringatomsorgroups Tetramethylsilane(TMS)achemicalshiftreferenceusedinNMRspectroscopy becauseithasachemicalshiftof0.00ppm.

chemicalshift=0.00ppmbydefinition Whatisachemicalshift? ItiscontrolledbytheE(spinflipenergy),whichisdeterminedbythemagnitude ofthemagneticfieldatthenucleus. Forinstance: LowmagneticfieldsmallE(lowchemicalshift) HighmagneticfieldlargeE(highchemicalshift) Chemicalshift, ,isthedifferencebetweenthefrequencyofanuclearspinflipofthe nucleusinquestionandthenuclearspinflipofareferencemolecule,dividedbythe operatingfrequencyoftheNMRspectrometer.Inotherwords,itistheresonant frequencyofanucleuscomparedtoastandard.Thepositionandnumber(intensity) ofchemicalshiftscanhelpusdetermineamoleculesstructure.

 Achemicalshiftgraph:

Differentgroupswithininamoleculecanhavedifferentchemicalshifts,depending ontheirbondsandtheatomsattached. Whatfactorscausechemicalshifts? 1.ElectronDensity: Ingeneral, higherelectrondensitylowerchemicalshift lowerelectrondensityhigherchemicalshift Highelectrondensityofneighboringatomsmayshieldthenucleusfromanexternal magneticfield.Ifthereislittleornoelectrondensityinnearbyatomsorgroups,the nucleuscanalsobedeshielded. Whatisshieldinganddeshielding? Shieldingiswhenthenucleusexperiencesaweakermagneticfieldaroundit.This canbecausedbyotheratomsgettinginthewayofthenucleusandthemagnetic field,orthenucleusitselfhavingalowspinflipenergy.Duetotheweakermagnetic fielditexperiences,anucleuswithmoreshieldingwillhavealowerppmand thereforelieontherightsideofthechemicalshiftscale. Deshieldingiswhenthenucleusexperiencesahighermagneticfieldaroundit.This canbeduetoitsproximitytoastrongmagneticfieldorhavingitselfahighspinflip energy.Becauseofitshighmagneticfield,amoredeshieldednucleuswillhavea higherppmandthereforelieontheleftsideofthechemicalshiftscale.

 MoreDeshielded

ChemicalShiftScale(ppm)

MoreShielded

2.Electronegativity: ThehighertheelectronegativitydifferencebetweenHanditssurroundingatoms, thehigherthechemicalshift.Thisisbecausethehighertheelectronegativity differencebetweenHandanotheratom,thelowertheelectrondensityisaround theH(proton),andthusthemoredeshieldingtheprotonexperiences.Asaresult, theprotonwillhaveahigherchemicalshift. Forexample: IodinehasanENof2.5 BrominehasanENof2.8 ChlorinehasanENof3.0 FluorinehasanENof4.0 HydrogenhasanENof2.1

TheHIbondistheleastelectronegativeandtheHFbondisthemost electronegative.So,intermsofchemicalshifts,HI<HBr<HCl<HF. LessENdifference,solowerchemicalshift

MoreENdifference,sohigherchemicalshift OtherTrends: Electronegativityeffectsdecreasewithincreasingdistance:

Asthehydrogensmovefartherawayfromchlorine,themostelectronegative atominthemolecule,theyexperiencemoreshieldingduetotheother hydrogensintheway.Asaresult,theHashaveasignificantlyhigherchemical shift(3.42ppm),thantheHds(0.92ppm).

Inamethanemolecule,themoreRgroupsthatareattachedtothecentral carbonatom,themoreelectronegativethemoleculeis,andthereforethe higherthechemicalshift. R3CH>RCH2R>RCH3 becausetheENoftheRgroupisgreaterthantheENofhydrogen. (WhateverRis,itwillhaveagreaterelectronegativitythanH).

ExtraExample: VisualrepresentationofCHchemicalshiftsindifferentmolecules: cyclo hexane aldehyde alkene nitro benzene

TMS,0 ppm

Increasingchemicalshift

PPM

Decreasingchemicalshift

 Itisimportanttonotethatthepositionofsignalsisdifferentfromtherelative intensityofthesignalsorpeaks.Thepositioniswhathasbeendiscussedhere:itis dependentuponshieldingandelectronegativityofnearbyatoms.Theintensityis proportionaltotherelativenumberofequivalentprotonsthereareinone positionitisrelatedtothemeasurementoftheareaunderthepeak,calculatedby integration. PracticeProblem: Whichofthefollowinghasthehighestchemicalshift?Whichhasthelowest?

Solution: 1.CH3FFluorineisthemostelectronegativeatom(EN=4.0).Therefore,intheCF bond,theareaofelectrondensityisaroundtheF,sothereislessprotondensity aroundCandsurroundingHs(protons).Asaresult,thereismoredeshielding(or lessshielding)aroundtheprotons,causingtheretobeagreatchemicalshift. OxygenhasanENof3.5,andbrominehasanENof2.8.OxygenhasagreaterEN WorksCited: "TheBasisforDifferencesinChemicalShifts."UCDavisChemWiki.3Aug.2011.Web. 11May2012.<http://chemwiki.ucdavis.edu>. "ChemicalShift."Wikipedia.WikimediaFoundation,05Nov.2011.Web.11May 2012.<http://en.wikipedia.org/wiki/Chemical_shift>. Hardinger,Steven.Chemistry14CLectureSupplement.Fifthed.Plymouth,MI: HaydenMcNeil,2011. Hardinger,Steven."UCLAChemistryandBiochemistry."OrganicChemistryatUCLA. UCLAChemistryandBiochemistry.Web.11May2012. <http://www.chem.ucla.edu/harding/index.html>. "NuclearMagneticResonanceSpectroscopy."NMRSpectroscopy.Web.12May2012. <http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Spectrpy/nm r/nmr1.htm>.