0.2 Nmr spin coupling  (Page 6/3)

The basis of spin coupling

Nuclear magnetic resonance (NMR) signals arise when nuclei absorb a certain radio frequency and are excited from one spin state to another. The exact frequency of electromagnetic radiation that the nucleus absorbs depends on the magnetic environment around the nucleus. This magnetic environment is controlled mostly by the applied field, but is also affected by the magnetic moments of nearby nuclei. Nuclei can be in one of many spin states ( [link] ), giving rise to several possible magnetic environments for the observed nucleus to resonate in. This causes the NMR signal for a nucleus to show up as a multiplet rather than a single peak.

When nuclei have a spin of I = ¹ / ₂ (as with protons), they can have two possible magnetic moments and thus split a single expected NMR signal into two signals. When more than one nucleus affects the magnetic environment of the nucleus being examined, complex multiplets form as each nucleus splits the signal into two additional peaks. If those nuclei are magnetically equivalent to each other, then some of the signals overlap to form peaks with different relative intensities. The multiplet pattern can be predicted by Pascal’s triangle ( [link] ), looking at the n ^th row, where n = number of nuclei equivalent to each other but not equivalent to the one being examined. In this case, the number of peaks in the multiplet is equal to n + 1

When there is more than one type of nucleus splitting an NMR signal, then the signal changes from a multiplet to a group of multiplets ( [link] ). This is caused by the different coupling constants associated with different types of nuclei. Each nucleus splits the NMR signal by a different width, so the peaks no longer overlap to form peaks with different relative intensities.

When nuclei have I> ¹ / ₂ , they have more than two possible magnetic moments and thus split NMR signals into more than two peaks. The number of peaks expected is 2I + 1, corresponding to the number of possible orientations of the magnetic moment. In reality however, some of these peaks may be obscured due to quadrupolar relaxation. As a result, most NMR focuses on I = ¹ / ₂ nuclei such as ¹ H, ¹³ C, and ³¹ P.

Multiplets are centered around the chemical shift expected for a nucleus had its signal not been split. The total area of a multiplet corresponds to the number of nuclei resonating at the given frequency.

Spin coupling in molecules

Looking at actual molecules raises questions about which nuclei can cause splitting to occur. First of all, it is important to realize that only nuclei with I ≠ 0 will show up in an NMR spectrum. When I = 0, there is only one possible spin state and obviously the nucleus cannot flip between states. Since the NMR signal is based on the absorption of radio frequency as a nucleus transitions from one spin state to another, I = 0 nuclei do not show up on NMR. In addition, they do not cause splitting of other NMR signals because they only have one possible magnetic moment. This simplifies NMR spectra, in particular of organic and organometallic compounds, greatly, since the majority of carbon atoms are ¹² C, which have I = 0.