2 DNMR Coupling Constants Geminal Coupling are usually
- Slides: 36
2 DNMR
Coupling Constants Geminal Coupling are usually negative: CH 2 Vicinal coupling usually positive: CH-CH Why? Coupling is through bonding electrons; consider the following model
2 D NMR basically provides information about connectivity and proximity COSY spectroscopy (correlation spectroscopy) (various pulse sequences are available providing similar information)
HH COSY
H H COSY-90
Long range HH COSY
H C COSY HSQC method
gradient select HMQC method gradient select HMBC method
2. Off-resonance decoupling
2 NOE enhancement observed
13 C NMR Coupling is reduced, but multiplicity is retained; 1 H irradiation 1 ppm upfield from TMS; to observe multiplicity at C-3, 1 H irradiation could be set to 10 ppm downfield from TMS
signals can be integrated
Demonstration of the effect of NOE on decoupling
C-9 signal as a function of H decoupling C-9
3. Attached protons
4. Identification of nearest neighbors
HH Identification of 1, 1’-Me Identification of 5 -Me Identification of H 4 Identification of 10 -Me Identification of H 3 Identification of H 2 p=3 q=2
Selective Decoupling irradiate H 4 doublet triplet little interaction normal spectrum
Results are often reported as difference spectra
10 Note: peak s 2 and 3 are mislabeled
Measurement of CH coupling constants Heteronuclear J resolved Spectrum
Identify the carbons by chemical shift i j h d f e ab g c
Let test our assignments using ACD
An INADEQUATE spectrum (incredible natural abundance double quantum transfer experiment spectroscopy) measures 13 C – 13 C transfer of magnetization between two 13 C nuclei using natural abundance C (detection of 1 in 10000 molecules). j i j h i i h f g e d f g d c f e a, b
AX 3 XAM 2 where JAX= JAM JXM = 0
Can we assign the peaks? carbon count
2 =CC 2 =CH 1 3 CH 3 2 CH 2
8, 9, 10 1 4, 5 2, 6
NOE Difference Spectra Some NOE operates through space as well as through bonding electrons. The through space interaction decreases as the inverse of the sixth power of the through space distance of the nuclei. The through space interaction occurs between nuclei that interact by a dipolar interaction The NOE difference spectrum is obtained by subtracting a normal spectrum from one in which a specific proton is irradiated. An measurable interaction can be expected up to about 4Å.
9 b a bb a 2 6 irradiated
10 9 8 b c a irradiated 2 6 c Irradiated b irradiated a
irradiated
1 5 4
13 C NMR 1 4, 5 9, 10, 8 3, 7 2, 6 8 9, 10 4 5 OH 1 H NMR 1 6 2
- Spin-spin coupling examples
- Geminal and vicinal coupling constants
- Factors affecting chemical shift in nmr spectroscopy
- Geminal coupling
- Enantiotopic protons
- Geminal coupling
- Mikael ferm
- Vicinal dihalide
- Toughness on a stress strain curve
- Constant in avogadro's law
- How to convert kp to kc
- Rc time constants
- What is
- Mark overmars game maker
- Constant scientific method
- Crystal binding and elastic constants
- Ideal gas conditions
- Crystal binding energy
- Named constants in java
- Activity equilibrium constant
- Rc time constant
- Constant math
- Constants in scientific method
- Acceleration error constant
- C chart six sigma
- Equilibrium constant
- Const in c#
- E matlab constant
- Software engineering road map
- Focus figure 9.1 events at the neuromuscular junction
- Cross frequency coupling
- Function of flexible coupling
- Csc 205
- Half lap muff coupling drawing
- Coupling capacitance
- Hn ha
- Grasp principles