Proton nuclear magnetic resonance (proton NMR, hydrogen-1 NMR, or 1H NMR) is the application of nuclear magnetic resonance in NMR spectroscopy with respect to hydrogen-1 nuclei within the molecules of a substance, in order to determine the structure of its molecules. In samples where natural hydrogen (H) is used, practically all the hydrogen consists of the isotope 1H (hydrogen-1; i.e. having a proton for a nucleus). Simple NMR spectra are recorded in solution, and solvent protons must not be allowed to interfere. Deuterated (deuterium = 2H, often symbolized as D) solvents especially for use in NMR are preferred, e.g. deuterated water, D2O, deuterated acetone, (CD3)2CO, deuterated methanol, CD3OD, deuterated dimethyl sulfoxide, (CD3)2SO, and deuterated chloroform, CDCl3. However, a solvent without hydrogen, such as carbon tetrachloride, CCl4 or carbon disulfide, CS2, may also be used. Historically, deuterated solvents were supplied with a small amount (typically 0.1%) of tetramethylsilane (TMS) as an internal standard for referencing the chemical shifts of each analyte proton. TMS is a tetrahedral molecule, with all protons being chemically equivalent, giving one single signal, used to define a chemical shift = 0 ppm. It is volatile, making sample recovery easy as well. Modern spectrometers are able to reference spectra based on the residual proton in the solvent (e.g. the CHCl3, 0.01% in 99.99% CDCl3). Deuterated solvents are now commonly supplied without TMS. Deuterated solvents permit the use of deuterium frequency-field lock (also known as deuterium lock or field lock) to offset the effect of the natural drift of the NMR's magnetic field B 0 {\displaystyle B_{0}} . In order to provide deuterium lock, the NMR constantly monitors the deuterium signal resonance frequency from the solvent and makes changes to the B 0 {\displaystyle B_{0}} to keep the resonance frequency constant. Additionally, the deuterium signal may be used to accurately define 0 ppm as the resonant frequency of the lock solvent and the difference between the lock solvent and 0 ppm (TMS) are well known. Proton NMR spectra of most organic compounds are characterized by chemical shifts in the range +14 to -4 ppm and by spin–spin coupling between protons. The integration curve for each proton reflects the abundance of the individual protons. Simple molecules have simple spectra. The spectrum of ethyl chloride consists of a triplet at 1.5 ppm and a quartet at 3.5 ppm in a 3:2 ratio. The spectrum of benzene consists of a single peak at 7.2 ppm due to the diamagnetic ring current. Together with carbon-13 NMR, proton NMR is a powerful tool for molecular structure characterization.
Chemical shifts Chemical shift values, symbolized by δ, are not precise, but typical – they are to be therefore regarded mainly as a reference. Deviations are in ±0.2 ppm range, sometimes more. The exact value of chemical shift depends on molecular structure and the solvent, temperature, magnetic field in which the spectrum is being recorded and other neighboring functional groups. Hydrogen nuclei are sensitive to the hybridization of the atom to which the hydrogen atom is attached and to electronic effects. Nuclei tend to be deshielded by groups that withdraw electron density. Deshielded nuclei resonate at higher δ values, whereas shielded nuclei resonate at lower δ values. Examples of electron withdrawing substituents are −OH, −OCOR, −OR, −NO2 and halogens. These cause a downfield shift of approximately 2–4 ppm for H atoms on Cα (an aliphatic C atom directly bonded to the substituent in question) and of less than 1–2 ppm for H atoms on Cβ (an aliphatic C atom bonded to Cα). Carbonyl groups, olefinic fragments and aromatic rings contribute sp2 hybridized carbon atoms to an aliphatic chain. This causes a downfield shift of 1–2 ppm at Cα. Note that labile protons (−OH, −NH2, −SH) have no characteristic chemical shift. However, such resonances can be identified by the disappearance of a peak when reacted with D2O, as deuterium will replace a protium atom. This method is called a D2O shake. Acidic protons may also be suppressed when a solvent containing acidic deuterium ions (e.g. methanol-d4) is used. An alternate method for identifying protons that are not attached to carbons is the heteronuclear single quantum coherence (HSQC) experiment, which correlates protons and carbons that are one bond away from each other. A hydrogen that is not attached to a carbon can be identified because it does not have a crosspeak in the HSQC spectrum.
Signal intensity
The integrated intensities of NMR signals are, ideally, proportional to the ratio of the nuclei within the molecule. Together with chemical shift and coupling constants, the integrated intensities allow structural assignments. For mixtures, the signal intensities can be used to determine molar ratios. These considerations are valid only when sufficient time is allowed for full relaxation of the affected signals, as determined by their T1 values. A further complication arises from the difficulty of integrating signals of very different line shapes.
Spin–spin couplings
In addition to chemical shift, NMR spectra allow structural assignments by virtue of spin–spin coupling (and integrated intensities). Because nuclei themselves possess a small magnetic field, they influence each other, changing the energy and hence frequency of nearby nuclei as they resonate—this is known as spin–spin coupling. The most important type in basic NMR is scalar coupling. This interaction between two nuclei occurs through chemical bonds, and can typically be seen up to three bonds away (3-J coupling), although it can occasionally be visible over four to five bonds, though these tend to be considerably weaker.
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