Spin-Spin Interactions

The nmr spectrum of 1,1-dichloroethane (below right) is more complicated than we might have expected from the previous examples. Unlike its 1,2-dichloro-isomer (below left), which displays a single resonance signal from the four structurally equivalent hydrogens, the two signals from the different hydrogens are split into close groupings of two or more resonances. This is a common feature in the spectra of compounds having different sets of hydrogen atoms bonded to adjacent carbon atoms. The signal splitting in proton spectra is usually small, ranging from fractions of a Hz to as much as 18 Hz, and is designated as J (referred to as the coupling constant). In the 1,1-dichloroethane example all the coupling constants are 6.0 Hz, as illustrated by clicking on the spectrum.

1,2-dichloroethane		1,1-dichloroethane

The splitting patterns found in various spectra are easily recognized, provided the chemical shifts of the different sets of hydrogen that generate the signals differ by two or more ppm. The patterns are symmetrically distributed on both sides of the proton chemical shift, and the central lines are always stronger than the outer lines. The most commonly observed patterns have been given descriptive names, such as doublet (two equal intensity signals), triplet (three signals with an intensity ratio of 1:2:1) and quartet (a set of four signals with intensities of 1:3:3:1). Four such patterns are displayed in the following illustration. The line separation is always constant within a given multiplet, and is called the coupling constant (J). The magnitude of J, usually given in units of Hz, is magnetic field independent.

The splitting patterns shown above display the ideal or "First-Order" arrangement of lines. This is usually observed if the spin-coupled nuclei have very different chemical shifts (i.e. Δν is large compared to J). If the coupled nuclei have similar chemical shifts, the splitting patterns are distorted (second order behavior). In fact, signal splitting disappears if the chemical shifts are the same. Two examples that exhibit minor 2nd order distortion are shown below (both are taken at a frequency of 90 MHz). The ethyl acetate spectrum on the left displays the typical quartet and triplet of a substituted ethyl group. The spectrum of 1,3-dichloropropane on the right demonstrates that equivalent sets of hydrogens may combine their influence on a second, symmetrically located set.
Even though the chemical shift difference between the A and B protons in the 1,3-dichloroethane spectrum is fairly large (140 Hz) compared with the coupling constant (6.2 Hz), some distortion of the splitting patterns is evident. The line intensities closest to the chemical shift of the coupled partner are enhanced. Thus the B set triplet lines closest to A are increased, and the A quintet lines nearest B are likewise stronger. A smaller distortion of this kind is visible for the A and C couplings in the ethyl acetate spectrum.

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