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l lM8 Soectoscooy
ClM 244 - Cgan|c C|em|sty ll
M|se|coo|a bn|ves|ty
L. lan| ?eoez Casn||o
So|ng 2014
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1yoes o Soectoscooy
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L|eent eg|ons o t|e e|ectomagnenc soectum ae useo to
oobe o|eent asoects o mo|ecu|a stuctue
Magnenc oooenes o luc|e|
1|e so|nn|ng c|age |n t|e
nuc|eus ceates a MAClL1lC
MCMLl1 (Magnenc e|o)
S
luc|ea so|n 8 Lxtena| Magnenc l|e|os
/
luc|ea so|n 8 Lxtena| Magnenc l|e|os
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lnstumentanon (Connnuous vave)
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lnstumentanon (l1 lM8)
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lnstumentanon (l1 lM8)
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C|em|ca| S||s
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! Legee o s||e|o|ng w||| oeoeno on t|e oens|ty o t|e e|ecton
c|ouo c|cu|anng aouno a nuc|eus
! 1|e o|eence |n t|e absoonon oos|non o a oancu|a ooton
om t|e absoonon oos|non o a !"#"!"$%" ooton |s ca||eo t|e
%&"'(%)* ,&(- o t|e oancu|a ooton
C|em|ca| S||s
2S
Anyt||ng t|at aects t|e oens|ty o t|e e|ecton
c|ouo aouno a oancu|a nuc|eus w||| aect |ts
c|em|ca| s||:
! L|ectoneganv|ty eects (|noucnon)
! lyb|o|zanon eects (|noucnon)
! Ac|o|ty ano exc|angeab|e ootons, l-bono|ng
! Magnenc An|sotooy
C|em|ca| S||s
! lotons |n o|eent c|em|ca| env|onments ae s||e|oeo by
o|eent amounts
! 1|e |yooxy| ooton |s not s||e|oeo as muc| as t|e met|y|
ootons so t|e |yooxy| ooton absobs at a |owe e|o t|an
t|e met|y| ootons
! ve say t|at t|e ooton |s oes||e|oeo somew|at by t|e
oesence o t|e e|ectoneganve oxygen atom.
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C|em|ca| S||s
2/
lM8 S|gna|s
! 1|e !"#$%& o s|gna|s s|ows |ow many o|eent
||nos o ootons ae oesent
! 1|e '()*+(! o t|e s|gna|s s|ows |ow s||e|oeo o
oes||e|oeo t|e ooton |s
! 1|e ,!-%!.,-/ o t|e s|gna| s|ows t|e numbe o
ootons o t|at tyoe
! 1|e .0',1!2 s|ows t|e numbe o ootons on
aoacent atoms
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C|em|ca| S||s
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1|e most genea||y useu| eeence
comoouno |s tetamet|y|s||ane (1MS)
1|e zeo on t|e lM8 sca|e |s oeneo by
t|e oos|non o t|e oea| o 1MS.
1|e c|em|ca| s|| |s a measue o |ow a t|e s|gna| |s om
t|e eeence s|gna|
1|e common sca|e o c|em|ca| s||s |s |e ! (oe|ta) sca|e
!! # #$%&$'()*+,-.(' /0(12(,34 5/ .6( *,).027(,.
#8$%&
C|em|ca| S||s
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C|em|ca| S||s
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C|em|ca||y equ|va|ent ootons: ootons |n t|e same c|em|ca|
env|onment
Lac| set o c|em|ca||y equ|va|ent ootons |n a comoouno
g|ves |se to a s|gna| |n an 1l lM8 soectum o t|at
comoouno
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1
l lM8 soectum o 1-bomo-2,2-
o|met|y|oooane
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lumbe o s|gna|s

Lqu|va|ent ls |ave t|e

same c|em|ca| s||
1
l lM8 soectum o 1-bomo-2,2-
o|met|y|oooane
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C|em|ca| S||s
3S
C|em|ca| S||s - Magnenc An|sotooy
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C|em|ca| S||s - Magnenc An|sotooy
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C|em|ca| S||s - Magnenc An|sotooy
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lntega|s ano lnteganon
ln t|e lM8 soectum, t|e aea unoe eac|
oea| |s oooonona| to t|e numbe o
|yoogens geneanng t|at oea|.
1|e |nteganon te||s us t|e e|anve numbe o
ootons t|at g|ve |se to eac| s|gna|, not t|e
abso|ute numbe

4S
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l lM8 soectum o 1-bomo-2,2-
o|met|y|oooane
4/
low many |yoogens`
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lntega|s ano lnteganon
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So||mng o t|e s|gna|s
! An
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l lM8 s|gna| |s so||t |nto / - 1 oea|s, w|ee /
|s t|e numbe o equ|va|ent ootons bonoeo to
aoacent cabons
! Couo|eo ootons so||t eac| ot|e's s|gna|
! 1|e numbe o oea|s |n a s|gna| |s ca||eo t|e
mu|no||c|ty o t|e s|gna|
! 1|e so||mng o s|gna|s, causeo by so|n-so|n
couo||ng, occus w|en o|eent ||nos o ootons
ae c|ose to one anot|e
S4
So||mng o t|e s|gna|s
lt |s not t|e numbe o ootons g|v|ng |se to a s|gna|
t|at oetem|nes t|e mu|no||c|ty o t|e s|gna|
lt |s t|e numbe o ootons bonoeo to t|e
|mmeo|ate|y aoacent cabons t|at oetem|nes t|e
mu|no||c|ty

S6
So||mng o t|e s|gna|s
Lqu|va|ent ootons oo not so||t eac| ot|e's s|gna|
S/
S8
S9
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So|n Couo||ng, Mu|no|ets
ano So|n Systems
So|n Couo||ng, Mu|no|ets ano So|n Systems
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So||mng o t|e s|gna|s
So||mng |s obseveo | t|e ootons ae seoaateo by no moe
t|an t|ee " bonos
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Long-range
coupling occurs
over # systems,
such as benzene
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So|n Couo||ng, Mu|no|ets ano So|n Systems
6S
So|n Couo||ng, Mu|no|ets ano So|n Systems
6/
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/0
/1
Couo||ng Constants
1|e couo||ng constant (0) |s t|e o|stance between two
aoacent oea|s o a so||t lM8 s|gna| (|n lz)
/2
Coupled
protons have
the same
coupling
constant
1yo|ca|
1
l-lM8 Absoonons by tyoe o comoounos
/4
1yo|ca|
1
l-lM8 Absoonons by tyoe o comoounos
/S
1yo|ca|
1
l-lM8 Absoonons by tyoe o comoounos
/6
1yo|ca|
1
l-lM8 Absoonons by tyoe o comoounos
//
1yo|ca|
1
l-lM8 Absoonons by tyoe o comoounos
/8
1yo|ca|
1
l-lM8 Absoonons by tyoe o comoounos
/9
1yo|ca|
1
l-lM8 Absoonons by tyoe o comoounos
80
1yo|ca|
1
l-lM8 Absoonons by tyoe o comoounos
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1yo|ca|
1
l-lM8 Absoonons by tyoe o comoounos
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1yo|ca|
1
l-lM8 Absoonons by tyoe o comoounos
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1yo|ca|
1
l-lM8 Absoonons by tyoe o comoounos
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Summay
! 1|e numbe o c|em|ca| s||s (!) soec|y t|e
numbe o o|snnct ooton env|onments |n t|e
comoouno
! 1|e c|em|ca| s|| (!) va|ues soec|y t|e natue o
t|e c|em|ca| env|onment: a||y|, a||ene, etc.
! 1|e |nteganon va|ues soec|y t|e e|anve numbe
o ootons o eac| s|gna|
! 1|e so||mng soec|es t|e numbe o ne|g|bo|ng
ootons
! 1|e couo||ng constants soec|y t|e o|entanon o
t|e couo|eo ootons
8S