Spin Decoupling

We have noted that rapidly exchanging hydroxyl hydrogens are not spin-coupled to adjacent C-H groups. The reason for this should be clear. As each exchange occurs, there will be an equal chance of the new proton having a +1/2 or a ^_1/2 spin (remember that the overall populations of the two spin states are nearly identical). Over time, therefore, the hydroxyl hydrogen behaves as though it is rapidly changing its spin, and the adjacent nuclei see only a zero spin average from it. If we could cause other protons in a molecule to undergo a similar spin averaging, their spin-coupling influence on adjacent nuclei would cease. Such nmr experiments are possible, and are called spin decoupling.
When a given set of nuclei is irradiated with strong rf energy at its characteristic Larmor frequency, spin saturation and rapid interconversion of the spin states occurs. Neighboring nuclei with different Larmor frequencies are no longer influenced by specific long-lived spins, so spin-spin signal splitting of the neighbors vanishes. The following spectrum of 1-nitropropane may be used to illustrate this technique. The three distinct sets of hydrogens in this molecule generate three resonance signals (two triplets and a broad sextet). A carefully tuned decoupling signal may be broadcast into the sample while the remaining spectrum is scanned. The region of the decoupling signal is obscured, but resonance signals more than 60 Hz away may still be seen. By clicking on one of the three signals in the spectrum, the results of decoupling at that frequency will be displayed.

In this example, the nuclei being decoupled and the nuclei being observed by the spectrometer are of the same kind (both protons). We call this homonuclear decoupling. It is also possible to decouple different kinds of nuclei. For example, a compound having both hydrogen and fluorine as part of its molecular composition may exhibit spin-coupling between their nuclei, and one may be decoupled while the other is observed. This is termed heteronuclear decoupling. Heteronuclear decoupling is very important in ¹³C nmr spectroscopy.

مواضيع ذات صلة

Spectroscopic Properties of Alkynes

Spectroscopic Properties of Alkenes

Application of Chemical Shifts to Structure Determination

Correlations Between Structure and Chemical Shifts

Electronegativity and Chemical Shifts

Effects of Carbon Bond Type

Mass Spectroscopy

Hydrogen Bonding

Chemical Exchange

Proton-Proton Splittings and Conformational Analysis

Spin-Spin Splitting - What We Observe

Proton-Proton Splittings and Chemical Exchange