In organic chemistry, a carboxylate is the

conjugate base A conjugate acid, within the Brønsted–Lowry acid–base theory, is a chemical compound formed when an acid donates a proton () to a base—in other words, it is a base with a hydrogen ion added to it, as in the reverse reaction it loses a ...

of a

carboxylic acid In organic chemistry, a carboxylic acid is an organic acid that contains a carboxyl group () attached to an R-group. The general formula of a carboxylic acid is or , with R referring to the alkyl, alkenyl, aryl, or other group. Carboxylic ...

, (or ). It is an

ion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conv ...

with

negative charge Electric charge is the physical property of matter that causes charged matter to experience a force when placed in an electromagnetic field. Electric charge can be ''positive'' or ''negative'' (commonly carried by protons and electrons respectiv ...

. Carboxylate salts are

salts In chemistry, a salt is a chemical compound consisting of an ionic assembly of positively charged cations and negatively charged anions, which results in a compound with no net electric charge. A common example is table salt, with positively cha ...

that have the general formula , where M is a metal and ''n'' is 1, 2,...; ''carboxylate esters'' have the general formula (or ). R and R′ are organic groups; R′ ≠ H.

Synthesis

Carboxylate ions can be formed by deprotonation of carboxylic acids. Such acids typically have p''K''_a of less than 5, meaning that they can be deprotonated by many bases, such as sodium hydroxide or sodium bicarbonate. :RCOOH + NaOH -> RCOONa + H2O

Resonance stabilization of the carboxylate ion

Carboxylic acids easily dissociate into a carboxylate anion and a positively charged hydrogen ion (proton), much more readily than alcohols do (into an

alkoxide In chemistry, an alkoxide is the conjugate base of an alcohol and therefore consists of an organic group bonded to a negatively charged oxygen atom. They are written as , where R is the organic substituent. Alkoxides are strong bases and, wh ...

ion and a proton), because the carboxylate ion is stabilized by resonance. The negative charge that is left after deprotonation of the carboxyl group is delocalized between the two

electronegative Electronegativity, symbolized as , is the tendency for an atom of a given chemical element to attract shared electrons (or electron density) when forming a chemical bond. An atom's electronegativity is affected by both its atomic number and the ...

oxygen atoms in a resonance structure. If the R group is an electron-withdrawing group (such as –CF₃), the basicity of the carboxylate will be further weakened. : Carboxylate-resonance-2D

This

delocalization In chemistry, delocalized electrons are electrons in a molecule, ion or solid metal that are not associated with a single atom or a covalent bond.IUPAC Gold Boo''delocalization''/ref> The term delocalization is general and can have slightly diff ...

of the electron cloud means that both of the oxygen atoms are less strongly negatively charged; the positive proton is therefore less strongly attracted back to the carboxylate group once it has left; hence, the carboxylate ion is more stable and less basic as a result of resonance stabilization of the negative charge. In contrast, an

ion, once formed, would have a strong negative charge localized on its lone oxygen atom, which would strongly attract any nearby protons (indeed, alkoxides are very strong bases). Because of resonance stabilization, carboxylic acids have much lower p''K''_a values (and are therefore stronger acids) than

alcohols In chemistry, an alcohol is a type of organic compound that carries at least one hydroxyl () functional group bound to a saturated carbon atom. The term ''alcohol'' originally referred to the primary alcohol ethanol (ethyl alcohol), which is ...

. For example, the p''K''_a value of

acetic acid Acetic acid , systematically named ethanoic acid , is an acidic, colourless liquid and organic compound with the chemical formula (also written as , , or ). Vinegar is at least 4% acetic acid by volume, making acetic acid the main component ...

is 4.8, while ethanol has a p''K''_a of 16. Hence acetic acid is a much stronger acid than ethanol. This in turn means that for equimolar solutions of a carboxylic acid and an alcohol, the carboxylic acid would have a much lower pH.

Reactions

Nucleophilic substitution

Carboxylate ions are good

nucleophiles In chemistry, a nucleophile is a chemical species that forms bonds by donating an electron pair. All molecules and ions with a free pair of electrons or at least one pi bond can act as nucleophiles. Because nucleophiles donate electrons, they are ...

. They react with

alkyl halides The haloalkanes (also known as halogenoalkanes or alkyl halides) are alkanes containing one or more halogen substituents. They are a subset of the general class of halocarbons, although the distinction is not often made. Haloalkanes are widely us ...

to form ester. The following reaction shows the reaction mechanism. Ester-from-carboxylate-and-alkyl-halide-2D-skeletal

The nucleophilicity of carboxylate ions are much weaker than that of

hydroxide Hydroxide is a diatomic anion with chemical formula OH−. It consists of an oxygen and hydrogen atom held together by a single covalent bond, and carries a negative electric charge. It is an important but usually minor constituent of water. It ...

and

ions, but stronger than

halide In chemistry, a halide (rarely halogenide) is a binary chemical compound, of which one part is a halogen atom and the other part is an element or radical that is less electronegative (or more electropositive) than the halogen, to make a fluor ...

anions (in a

polar aprotic solvent A polar aprotic solvent is a solvent that lacks an acidic proton and is polar. Such solvents lack hydroxyl and amine groups. In contrast to protic solvents, these solvents do not serve as proton donors in hydrogen bonding In chemistry, a hydro ...

, though there are other effects such as solubility of the ion).

Reduction

Unlike the reduction of ester, the reduction of carboxylate is different, due to the lack of the leaving group and the relatively electron-rich carbon atom (due to the negative charge on the oxygen atoms). With a small amount of acid, the reaction occurs with lithium aluminium hydride by changing the LAH into the

Lewis acid A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any sp ...

AlH₃ in the process, converting the oxyanion to 4 Al–O bonds. Reaction of carboxylic acids reduction - part two

Reaction of carboxylic acids reduction - part three

Examples

This list is for cases where there is a separate article for the anion or its derivatives. All other organic acids should be found at their parent carboxylic acid. * Formate ion, HCOO⁻ *

Acetate An acetate is a salt formed by the combination of acetic acid with a base (e.g. alkaline, earthy, metallic, nonmetallic or radical base). "Acetate" also describes the conjugate base or ion (specifically, the negatively charged ion called an ...

ion, CH₃COO⁻ *

Methanetetracarboxylate In chemistry, methanetetracarboxylate is a tetravalent anion with formula or C(COO−)4. It has four carboxylate groups attached to a central carbon atom; so it has the same carbon backbone as neopentane. It is an oxocarbon anion, that is, c ...

ion, C(COO⁻)₄ * Oxalate ion,

References

{{Reflist Anions...........