In the previous chapter, we learned about three important analytical techniques which allow us to deduce information about the structure of an organic molecule. In IR spectroscopy, transitions in the vibrational states of covalent bonds lead to the absorbance of specific infrared frequencies, telling us about the presence or absence of functional groups in the molecule of interest. In UV-Vis spectroscopy, transitions in the energy levels of electrons in pi bonds lead to the absorbance of ultraviolet and visible light, providing us with information about the arrangement of double bonds in a molecule. And in mass spectrometry, we are usually able to learn the molecular weight of a sample molecule, in addition to other kinds of information from analysis of the masses of molecular fragments.
Although all three of these techniques provide us with valuable information about a molecule of interest, in most cases they do not – even in combination – tell us what we, as organic chemists, most want to know about our molecule. Specifically, these techniques do not allow us to determine its overall molecular structure – the framework, in other words, of its carbon-carbon and carbon-hydrogen bonds. It is this information that we need to have in order to be able to draw a Lewis structure of our molecule, and it is this information that is provided by an immensely powerful analytical technique called nuclear magnetic resonance (NMR) spectroscopy.
In NMR, the nuclei of hydrogen, carbon, and other important elements undergo transitions in their magnetic states, leading to the absorbance of radiation in the radio frequency range of the electromagnetic spectrum. By analyzing the signals from these transitions, we learn about the chemical environment that each atom inhabits, including information about the presence of neighboring atoms. In this chapter, we will see how information from NMR, especially when combined with data from IR, UV-Vis, and MS experiments, can make it possible for us to form a complete picture of the atom-to-atom framework of an organic molecule.
- 5.1: Prelude to Structure Determination
- One morning in a suburb of Edinburgh, Scotland, an active, athletic teenager named Charli found that she did not have her usual appetite for breakfast. She figured she was just feeling a little under the weather, and was not to worried. But as the days passed, her appetite did not return. Before long, she stopped eating lunch as well, and eventually she was hardly eating anything at all.
- 5.2: The Origin of the NMR Signal
- Nuclear magnetic resonance spectroscopy is an incredibly powerful tool for organic chemists because it allows us to analyze the connectivity of carbon and hydrogen atoms in molecules. The basis for NMR is the observation that many atomic nuclei generate their own magnetic field, or magnetic moment, as they spin about their axes.
- 5.3: Chemical Equivalence
- The frequency of radiation absorbed by a proton (or any other nucleus) during a spin transition in an NMR experiment is called its 'resonance frequency'. If all protons in all organic molecules had the same resonance frequency, NMR spectroscopy but would not be terribly useful for chemists.
- 5.4: The 1H-NMR experiment
- In an NMR experiment, a sample compound (we'll again use methyl acetate as our example) is placed inside a very strong applied magnetic field ( B0 ) generated by a superconducting magnet in the instrument. (The magnetic fields generated by modern NMR instruments are strong enough that users must take care to avoid carrying any magnetics objects anywhere near them.
- 5.5: The Basis for Differences in Chemical Shift
- We come now to the question of why nonequivalent protons have different resonance frequencies and thus different chemical shifts. The chemical shift of a given proton is determined primarily by interactions with the nearby electrons. The most important thing to understand is that when electrons are subjected to an external magnetic field, they form their own small induced magnetic fields in opposition to the external field.
- 5.6: Spin-Spin Coupling
- The 1H -NMR spectra that we have seen so far (of methyl acetate and 1,4-dimethylbenzene) are somewhat unusual in the sense that in both of these molecules, each set of protons generates a single NMR signal. In fact, the 1H -NMR spectra of most organic molecules contain proton signals that are 'split' into two or more sub-peaks.
- 5.7: 13C-NMR Spectroscopy
- The 12C isotope of carbon - which accounts for up about 99% of the carbons in organic molecules - does not have a nuclear magnetic moment, and thus is NMR-inactive. Fortunately for organic chemists, however, the 13C isotope, which accounts for most of the remaining 1% of carbon atoms in nature, has a magnetic dipole moment just like protons.
- 5.8: Solving Unknown Structures
- Now it is finally time to put together all that we have studied about structure determination techniques and learn how to actually solve the structure of an organic molecule 'from scratch' - starting, in other words, with nothing but the raw experimental data.
- 5.9: Complex Coupling in Proton Spectra
- In all of the examples of spin-spin coupling we saw in our discussion of proton NMR, the observed splitting resulted from the coupling of one set of protons to just one neighboring set of protons. When a set of protons is coupled to two sets of nonequivalent neighbors, with significantly different coupling constants, the result is a phenomenon called complex coupling.
- 5.10: Other Applications of NMR
- In the introduction to this chapter, we heard two stories about people whose lives were potentially saved when brain tumors were discovered during a magnetic resonance imaging (MRI) scan. MRI is a powerful diagnostic technique because it allows doctors to visualize internal body tissues while sparing the patient from surgery and potentially harmful, high energy x-rays.