Chapter 2

Modern NMR Spectroscopy

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Spin-spin Coupling, Spin-spin Splitting (N+1) Rule

spin-spin splitting : (n +1) rule (n: proton ) Ha: 2 proton: 2+1=3 peaks Hb: 1 proton: 1+1=2 peaks

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Spin-spin Coupling, Spin-spin Splitting (N+1) Rule proton A is coupled by proton B

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1H NMRSpin-Spin Splitting

Nuclear Magnetic Resonance Spectroscopy

Consider the spectrum below:

4 4

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Ethyl Bromide

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Spin-Spin Splitting in 1H NMR Spectra

Peaks are often split into multiple peaks due to

magnetic interactions between nonequivalent protons on adjacent carbons, The process is called spin-spin splitting
adjacent carbon(s), This is the n+1 rule

The splitting is into one more peak than the number of Hs on the The relative intensities are in proportion of a binomial distribution

given by Pascals Triangle

The set of peaks is a multiplet (2 = doublet, 3 = triplet, 4 = quartet,

5=pentet, 1 6=hextet, 7=heptet..) singlet

1 1 1 2 1 1 3 3 1 1 4 6 4 1 1 5 10 10 5 1 1 6 15 20 15 6 1
doublet triplet quartet pentet hextet heptet

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More deshielded

More shielded

X A .
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 coupling NMR spectrum ! 12C-H But, (13C 1.1%, 99% 12C) 13C-H J=215 Hz 13C (satelite) (carbon NMR )
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500 MHz NMR

Rules for Spin-Spin Splitting

Equivalent protons do not split each other

Protons that are farther than two carbon atoms apart do not

split each other

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1H NMRSpin-Spin Splitting
If Ha and Hb are not equivalent, splitting is observed when:

Splitting is not generally observed between protons separated by more than three bonds.

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The Origin of 1H NMRSpin-Spin Splitting

The frequency difference, measured in Hz, between two peaks of the doublet is called the coupling constant, J.

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The Origin of 1H NMRSpin-Spin Splitting

Let us now consider how a triplet arises:

Because there are two different ways to align one proton with B0, and one proton against B0that is, a b and abthe middle peak of the triplet is twice as intense as the two outer peaks, making the ratio of the areas under the three peaks 1:2:1. Two adjacent protons split an NMR signal into a 5/2/12 triplet.

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The Origin of 1H NMRSpin-Spin Splitting

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The Origin of 1H NMRSpin-Spin Splitting

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Nuclear Magnetic Resonance troscopy 1H NMRSpin-Spin Splitting

Spec-

Whenever two (or three) different sets of adjacent protons are equivalent to each other, use the n + 1 rule to determine the splitting pattern.

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Nuclear Magnetic Resonance troscopy 1H NMRSpin-Spin Splitting

Spec-

Whenever two (or three) different sets of adjacent protons are equivalent to each other, use the n + 1 rule to determine the splitting pattern.

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Nuclear Magnetic Resonance troscopy 1H NMRSpin-Spin Splitting

Spec-

Whenever two (or three) different sets of adjacent protons are not equivalent to each other, use the n + 1 rule to determine the splitting pattern only if the coupling constants (J) are identical:
Free rotation around C-C bonds averages coupling constant to J = 7Hz
c a a

Jab = Jbc

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Nuclear Magnetic Resonance troscopy 1H NMRSpin-Spin Splitting

Spec-

Whenever two (or three) different sets of adjacent protons are not equivalent to each other, use the n + 1 rule to determine the splitting pattern conly if the coupling constants (J) are identical:
a

c b

Jab = Jbc

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Nuclear Magnetic Resonance Spectroscopy 1H NMRStructure Determination

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Nuclear Magnetic Resonance Spectroscopy

1H NMRStructure Determination

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Nuclear Magnetic Resonance Spectroscopy 1H NMRStructure Determination

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1H NMRStructure Determination

Nuclear Magnetic Resonance Spectroscopy

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