Complulty of spectra

Overlap :pin.g of signa~:s an d spin co,upling

1 1 1 1

in creases comiplex,i ty of spie ctra

1

D,fifficult to interpret
 ·llQrJ -· IBA
.·•. __ ) ISolot'>e cxcl_u_iJ_·•y_c_"'- - - - - - - - - - ~ - - - - ~ = = = = =
·•.
'

1 N ,..1 R s·h i fl 1-clgent

I High fic1d strengths

Nuclear n1ag;nctic llot1bli.! r~~onanc'-3;

-· .

Sfiin :l:Jc-coup,l ing

I Spin t[tkHng .

- ·- - - - - - - - - - - - - - - - - - - - - - - - - - - -
'
- ~i":l\'lO OiinteJ111~i.ci.ruml~1~4lt ·
• • • ' • ■ • • • , • ., • • - ...
 ISOTOP EXCHANGE
• Deuteirium-heavy is oto pe of hydrogen
1
1 1

• Widely·used because of
easy introdu1rtion into th.e molecule
i·ts presence not detected in the spectrum
1

• Smaller magnetic 1 moment than hydrogen-absorlbs at

1

different fie[d strengths

• It broadens peak of neighbouring h1ydrcgen~lou1t does

not sprits-ccuples only slightly with 'hydrogen
1 1
 Ethy~ brom~de

• Deuterilum 2H SH
1rep1laces 1
m eth'y l J l1 111
Br-011~ 1
lhyd roge n.s 1H

Br-Ol1--cH1D
Ut
• Multiplicity of CH 2 •
DI IH
peaks changes
1 p 11 I
lr-Ol1-DID1
from quairtet to 1

211
triplet to doublet I
lt--al1~J
to singlet
PROTONS ON a-CARBON ATOMS 1"0 CARBONYL OR NITRO
1

GROUPS

il:'st· ·•r
l.;. - - C I 1i1'5,i·,nm ]
,£i. 1 ~- ,
1
1"•
.i '

u p1rnrurru; - tr~plet mprot11ns - n o

absorption

~ ,rolut11.5 - quru11lsel Pprutuns - tripl~l

y protons - triplet y protons - not

afffi!t.ed
 NMR Shift reagents

P.aramagnetic. -metal complexes

lEuropium (HO comple:x, Eu(DPM) 13 _ ]

Param1agnetic co mpd irnduce shift in the protons of molecule

1

l Chemical shift altered )

Spreads out nmr absorption patterns that overlap

l,..__ - ~~

Resolve clo:s ely- spa~ed signals

1

L
 Eg:- NMR spectrum of n~hexanol

a) Without shift reagent b) With shift reagent

 High field strength

• Chemical shi'ft difference between coupled protons

b,e come comparable to th1e coupling constant
1 1 1

-Ca 1use of com 1pl exity

1

• Achiew.ement of using liarger magnetic field

-spreading of IAv relative to J

• Spread out unresolved signals easily

1
Eg;-1-bromo-3-chl oro propane 1

a) 60 MHz spertra b) 180 MHz spe£tra

• I i
' -I
••• .,.
•

e
~91.11~·4.A,....,_t•tllllfIIJl,llltlllt•t~••'1!'-•..llilllllll!i.-
11 .. ..•
, ' •'ti , , .•• ,., ,, e t tats♦ '
 Nuclear Magnetic Double Resonance

SP IN DECOUPLING
1

• C,ou pli: ng between 1

lo1 Nainaal .,.c, -

neighlbo u1ring nucle1
1
i gives]
sp litting patterns-i1n some
1

"Va
cases com1plex patterns-
'tal I 1rrad,at•d
spin decoupling
• lrra1diation 0 f protons with 1

intense radi 0 frequency 1 1

lcJA· irrQdtalN
e ne rgy,-e Ii m1inates
1

com p Iete coup 11 ng

1 1
DOUBLE IRRADIATION OF AN AX
SPECTRU!\1

r,-+HX

f lb:bk 1rnd1111un or II,

Douhl, imdillion of 1n A1~5ptcllnlm
1
 Seconcl irra d_iatin,g freqL1enC)'
1

Sp-c,ctrL1m col~aps.ie! inco,mplet e 1

' Extra resonance lin es or residual splitting

1

-r,elatecl to er1ergy transitioJ1s of tl1e sp,i11 S}'Stem

I
o-bserv ed
1
INTERNUCLEAR DOUBLE RESONANCE
~ ~ ~«!NDOR!
Nlost po\vcrrul
douh]e
resnn nITT ce
tc-c.h~l iq;uc

1Qbsc1rvaliun11o f
Lh11: mu1iiplicily
of signaJs
hjddem by band
ovs:rlu~1~

Signals arc only

observed fi"om
coupl.cd
prolon-8.
 H0 ,& v1 fixed on one 01f the A
1

lines
X lines obscurre1d
~ Second weak perturbing
frequency(v2 }
Passes through hidden X lines
Change in intensity of A line
- ve or + ve signal
at positions ,corresponding to
X resonance frequencies