Scribd
Upload
405 views1 page

Dynam NMR

This document discusses dynamic NMR spectroscopy and the exchange rates between cis-trans isomers. It defines different exchange regimes - slow, intermediate, fast - based on the relationship between the exchange rate and chemical shift differences. It provides equations to calculate exchange rates and coalescence temperatures in each regime. The exchange rate depends on temperature according to the Arrhenius equation.

Uploaded by

Dana Capbun
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
405 views1 page

Dynam NMR

This document discusses dynamic NMR spectroscopy and the exchange rates between cis-trans isomers. It defines different exchange regimes - slow, intermediate, fast - based on the relationship between the exchange rate and chemical shift differences. It provides equations to calculate exchange rates and coalescence temperatures in each regime. The exchange rate depends on temperature according to the Arrhenius equation.

Uploaded by

Dana Capbun
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 1

Dynamic NMR

Example: cis-trans isomeriation


O
C H
3
N
CH
3
CH
3
O
C H
3
N
CH
3
CH
3
A
B
B
A
E t = h

E = h
1/2

1/2
=
E
h
=
1
2t
k
1
2
g() =
K(
A
-
B
)
2
( )
1
/
2
(
A
+
B
)-
2
+4
2

2
(
A
-)
2
(
B
-)
2
when (
A
)
o
1
/
2
) is negligible

A
B 1
/
2
( )

1
/
2
( )

A 1
/
2
( )

1
/
2
( )

e
e

B
= -

e
I
min
I
max
A. Slow Exchange
B. Intermediate
C. Coalescence
D. Fast Exchange
Slow Exchange:
(
A
)
o
1
/
2
=
1
2T
2A

g() =
KT

2A
'
1 + 4
2
T

2A
'
2
(
A
-)
2

Intermediate: >> (
,
-

B
)
-1
(
A
)
e
1
/
2
=
1
2T
2A

+
1
2

k =

]
1
(
A
)
e
1
/
2
-(
A
)
o
1
/
2
k =

2
[ ]
o
2
-
e
2
)
ratio method, r= I
max
/I
min
k =

o
2
(r + (r
2
- r )
1
/
2)
-
1
/
2

Coalescence Temperature:
k =

o
2

Fast Exchange: << (
,
-

B
)
-1
k =

o
2
2

1

]
1
(

1
/
2
)
e
-(
A
)
o
1
/
2
NMR time scale: k ~ 10
-1
-10
-5
s
-1
rotational barriers: 12-80 kJ/mole
g() =
KT

2
'
1 + 4
2
T

2
'
2
(
A
+
B
-2)
2
Temperature Dependence of the Exchange Rate
ln k = -
E
a
R

,
_
1
T
+ ln A

You might also like