thumb|upright=1.3|alt=An amino acid, illustrated in two different ionization states. First, it has a neutral amine and neutral carboxylic acid. Second, it has a protonated ammonium cation and deprotonated carboxylate anion.| The tautomers of an amino acid: (1) neutral and (2) [[zwitterionic forms]]
In chemistry, tautomers () are a subset of structural isomers (constitutional isomers) of chemical compounds that readily interconvert. The chemical reaction interconverting the two is called tautomerization. This conversion commonly results from the relocation of a hydrogen atom within the compound. The phenomenon of tautomerization is called tautomerism, also called desmotropism. Tautomerism is for example relevant to the behavior of amino acids and nucleic acids, two of the fundamental building blocks of life.
Care should be taken not to confuse tautomers with depictions of "contributing structures" in chemical resonance. Tautomers are distinct chemical species that can be distinguished by their differing atomic connectivities, molecular geometries, and physicochemical and spectroscopic properties, whereas resonance forms are merely alternative Lewis structure (valence bond theory) depictions of a single chemical species, whose true structure is a quantum superposition, essentially the "average" of the idealized, hypothetical geometries implied by these resonance forms.
The term tautomer is derived .
Examples
thumb|upright=2|right|Some examples of tautomers
thumb|upright=1.5|right|Keto-enol tautomerization typically strongly favors the keto tautomer, but an important exception is the case of 1,3-diketones such as [[acetylacetone. It is typically associated with polar molecules and ions containing functional groups that are at least weakly acidic. Most common tautomers exist in pairs, which means that the hydrogen is located at one of two positions, and even more specifically the most common form involves a hydrogen changing places with a double bond: . Common tautomeric pairs include:
- Ring–chain tautomers occur when the movement of the proton is accompanied by a change from an open structure to a ring, such as the open chain and cyclic hemiacetal (typically pyranose or furanose forms) of many sugars. It is distinct from prototropic tautomerism, and involves processes with rapid reorganisation of bonding electrons.
thumb|left|Oxepin – benzene oxide equilibrium
A pair of valence tautomers with formula C<sub>6</sub>H<sub>6</sub>O are benzene oxide and oxepin.
Other examples of this type of tautomerism can be found in bullvalene, and in open and closed forms of certain heterocycles, such as organic azides and tetrazoles, or mesoionic münchnone and acylamino ketene.
Valence tautomerism requires a change in molecular geometry and should not be confused with canonical resonance structures or mesomers.
Inorganic materials
In inorganic extended solids, valence tautomerism can manifest itself in the change of oxidation states its spatial distribution upon the change of macroscopic thermodynamic conditions. Such effects have been called charge ordering or valence mixing to describe the behavior in inorganic oxides.
Consequences for chemical databases
The existence of multiple possible tautomers for individual chemical substances can lead to confusion. For example, samples of 2-pyridone and 2-hydroxypyridine do not exist as separate isolatable materials: the two tautomeric forms are interconvertible and the proportion of each depends on factors such as temperature, solvent, and additional substituents attached to the main ring.
:2-pyridone-chemical-tautomer.svg
Historically, each form of the substance was entered into databases such as those maintained by the Chemical Abstracts Service and given separate CAS Registry Numbers. 2-Pyridone was assigned [142-08-5] and 2-hydroxypyridine [109-10-4]. The latter is now a "replaced" registry number so that look-up by either identifier reaches the same entry. The facility to automatically recognise such potential tautomerism and ensure that all tautomers are indexed together has been greatly facilitated by the creation of the International Chemical Identifier (InChI) and associated software. Thus the standard InChI for either tautomer is <code>
InChI=1S/C5H5NO/c7-5-3-1-2-4-6-5/h1-4H,(H,6,7)</code>.