organic chemistry Organic chemistry is a subdiscipline within chemistry involving the science, scientific study of the structure, properties, and reactions of organic compounds and organic matter, organic materials, i.e., matter in its various forms that contain ...

, triflate (

systematic name A systematic name is a name given in a systematic way to one unique group, organism, object or chemical substance, out of a specific population or collection. Systematic names are usually part of a nomenclature. A semisystematic name or semitrivi ...

: trifluoromethanesulfonate), is a

functional group In organic chemistry, a functional group is any substituent or moiety (chemistry), moiety in a molecule that causes the molecule's characteristic chemical reactions. The same functional group will undergo the same or similar chemical reactions r ...

with the

formula In science, a formula is a concise way of expressing information symbolically, as in a mathematical formula or a ''chemical formula''. The informal use of the term ''formula'' in science refers to the general construct of a relationship betwe ...

and

structure A structure is an arrangement and organization of interrelated elements in a material object or system, or the object or system so organized. Material structures include man-made objects such as buildings and machines and natural objects such as ...

. The triflate group is often represented by , as opposed to −Tf, which is the triflyl group, . For example, ''n''-butyl triflate can be written as . The corresponding triflate

anion 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 conven ...

, , is an extremely stable

polyatomic ion A polyatomic ion (also known as a molecular ion) is a covalent bonded set of two or more atoms, or of a metal complex, that can be considered to behave as a single unit and that usually has a net charge that is not zero, or in special c ...

; this comes from the fact that

triflic acid Triflic acid, the short name for trifluoromethanesulfonic acid, TFMS, TFSA, HOTf or TfOH, is a sulfonic acid with the chemical formula CF3SO3H. It is one of the strongest known acids. Triflic acid is mainly used in research as a catalyst for este ...

() is a

superacid In chemistry, a superacid (according to the original definition) is an acid with an acidity greater than that of 100% pure sulfuric acid (), which has a Hammett acidity function (''H''0) of −12. According to the modern definition, a superacid i ...

; i.e. it is more acidic than pure

sulfuric acid Sulfuric acid (American spelling and the preferred IUPAC name) or sulphuric acid (English in the Commonwealth of Nations, Commonwealth spelling), known in antiquity as oil of vitriol, is a mineral acid composed of the elements sulfur, oxygen, ...

, already one of the strongest

acid An acid is a molecule or ion capable of either donating a proton (i.e. Hydron, hydrogen cation, H+), known as a Brønsted–Lowry acid–base theory, Brønsted–Lowry acid, or forming a covalent bond with an electron pair, known as a Lewis ...

s known.

Applications

A triflate group is an excellent

leaving group In organic chemistry, a leaving group typically means a Chemical species, molecular fragment that departs with an electron, electron pair during a reaction step with heterolysis (chemistry), heterolytic bond cleavage. In this usage, a ''leaving gr ...

used in certain

organic reactions Organic reactions are chemical reactions involving organic compounds. The basic organic chemistry reaction types are addition reactions, elimination reactions, substitution reactions, pericyclic reactions, rearrangement reactions, photochemical r ...

such as

nucleophilic substitution In chemistry, a nucleophilic substitution (SN) is a class of chemical reactions in which an electron-rich chemical species (known as a nucleophile) replaces a functional group within another electron-deficient molecule (known as the electrophile) ...

Suzuki coupling The Suzuki reaction or Suzuki coupling is an organic reaction that uses a palladium complex catalyst to cross-couple a boronic acid to an organohalide. It was first published in 1979 by Akira Suzuki, and he shared the 2010 Nobel Prize in Chemis ...

s and

Heck reaction The Heck reaction (also called the Mizoroki–Heck reaction) is the chemical reaction of an unsaturated halide (or triflate) with an alkene in the presence of a base and a palladium catalyst to form a substituted alkene. It is named after T ...

s. Since alkyl triflates are extremely reactive in S_N2 reactions, they must be stored in conditions free of

nucleophile 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 ...

s (such as

water Water is an inorganic compound with the chemical formula . It is a transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance. It is the main constituent of Earth's hydrosphere and the fluids of all known liv ...

). The anion owes its stability to

resonance stabilization In chemistry, resonance, also called mesomerism, is a way of describing bonding in certain molecules or polyatomic ions by the combination of several contributing structures (or ''forms'', also variously known as ''resonance structures'' or '' ...

which causes the negative charge to be spread symmetrically over the three oxygen atoms. An additional stabilization is achieved by the

trifluoromethyl The trifluoromethyl group is a functional group that has the formula . The naming of is group is derived from the methyl group (which has the formula ), by replacing each hydrogen atom by a fluorine atom. Some common examples are trifluoromethane ...

group, which acts as a strong

electron-withdrawing group An electron-withdrawing group (EWG) is a Functional group, group or atom that has the ability to draw electron density toward itself and away from other adjacent atoms. This electron density transfer is often achieved by resonance or inductive effe ...

using the sulfur atom as a bridge. Triflates have also been applied as ligands for group 11 and 13 metals along with

lanthanide The lanthanide () or lanthanoid () series of chemical elements comprises at least the 14 metallic chemical elements with atomic numbers 57–70, from lanthanum through ytterbium. In the periodic table, they fill the 4f orbitals. Lutetium (el ...

Lithium triflate Lithium triflate (lithium triflouromethanesulfonate or LiOTf) is a salt with the chemical formula LiCF3SO3. It is composed of the lithium cation (Li+) and triflate anion (CF3SO3−; TfO−). It is very hygroscopic. The salt is used in lithium-ion ...

s are used in some

lithium ion batteries A lithium-ion or Li-ion battery is a type of rechargeable battery that uses the reversible intercalation of Li+ ions into electronically conducting solids to store energy. Li-ion batteries are characterized by higher specific energy, energy d ...

as a component of the

electrolyte An electrolyte is a substance that conducts electricity through the movement of ions, but not through the movement of electrons. This includes most soluble Salt (chemistry), salts, acids, and Base (chemistry), bases, dissolved in a polar solven ...

. A mild triflating reagent is phenyl triflimide or ''N'',''N''-bis(trifluoromethanesulfonyl)aniline, where the by-product is F₃SO₂N−Phsup>−.

Triflate salts

Triflate

salt In common usage, salt is a mineral composed primarily of sodium chloride (NaCl). When used in food, especially in granulated form, it is more formally called table salt. In the form of a natural crystalline mineral, salt is also known as r ...

s are thermally very stable with melting points up to 350 °C for

sodium Sodium is a chemical element; it has Symbol (chemistry), symbol Na (from Neo-Latin ) and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 element, group 1 of the peri ...

boron Boron is a chemical element; it has symbol B and atomic number 5. In its crystalline form it is a brittle, dark, lustrous metalloid; in its amorphous form it is a brown powder. As the lightest element of the boron group it has three ...

and

silver Silver is a chemical element; it has Symbol (chemistry), symbol Ag () and atomic number 47. A soft, whitish-gray, lustrous transition metal, it exhibits the highest electrical conductivity, thermal conductivity, and reflectivity of any metal. ...

salts especially in water-free form. They can be obtained directly from triflic acid and the metal hydroxide or metal carbonate in water. Alternatively, they can be obtained from reacting metal chlorides with neat triflic acid or

silver triflate Silver trifluoromethanesulfonate, or silver triflate is the triflate (CF3SO3−) salt of Ag+. It is a white or colorless solid that is soluble in water and some organic solvents including, benzene. It is a reagent used in the synthesis of organi ...

, or from reacting barium triflate with metal sulfates in water: : : : Metal triflates are used as

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 ...

catalysts in

. Especially useful are the lanthanide triflates of the type (where Ln is a

lanthanoid The lanthanide () or lanthanoid () series of chemical elements comprises at least the 14 Metal, metallic chemical elements with atomic numbers 57–70, from lanthanum through ytterbium. In the periodic table, they fill the 4f orbitals. Lutetium ...

). A related popular catalyst

scandium triflate Scandium trifluoromethanesulfonate, commonly called scandium triflate, is a chemical compound with formula Sc(SO3CF3)3, a salt (chemistry), salt consisting of scandium cations Sc3+ and triflate anions. Scandium triflate is used as a reagent in ...

is used in such reactions as

aldol reaction The aldol reaction (aldol addition) is a Chemical reaction, reaction in organic chemistry that combines two Carbonyl group, carbonyl compounds (e.g. aldehydes or ketones) to form a new β-hydroxy carbonyl compound. Its simplest form might invol ...

s and

Diels–Alder reaction In organic chemistry, the Diels–Alder reaction is a chemical reaction between a Conjugated system, conjugated diene and a substituted alkene, commonly termed the Diels–Alder reaction#The dienophile, dienophile, to form a substituted cyclohexe ...

s. An example is the

Mukaiyama aldol addition In organic chemistry, the Mukaiyama aldol addition is an organic reaction and a type of aldol reaction between a silyl enol ether () and an aldehyde () or formate (). The reaction was discovered by Teruaki Mukaiyama in 1973. His choice of react ...

reaction between

benzaldehyde Benzaldehyde (C6H5CHO) is an organic compound consisting of a benzene ring with a formyl substituent. It is among the simplest aromatic aldehydes and one of the most industrially useful. It is a colorless liquid with a characteristic almond-li ...

and the

silyl enol ether In organosilicon chemistry, silyl enol ethers are a class of organic compounds that share the common functional group , composed of an enolate () bonded to a silane () through its oxygen end and an ethene group () as its carbon end. They are i ...

cyclohexanone Cyclohexanone is the organic compound with the formula (CH2)5CO. The molecule consists of six-carbon cyclic molecule with a ketone functional group. This colorless oily liquid has a sweet odor reminiscent of benzaldehyde. Over time, samples of ...

with an 81%

chemical yield In chemistry, yield, also known as reaction yield or chemical yield, refers to the amount of product obtained in a chemical reaction. Yield is one of the primary factors that scientists must consider in organic and inorganic chemical synthesis ...

. The corresponding reaction with the

yttrium Yttrium is a chemical element; it has Symbol (chemistry), symbol Y and atomic number 39. It is a silvery-metallic transition metal chemically similar to the lanthanides and has often been classified as a "rare-earth element". Yttrium is almost a ...

salt fails: Triflate is a commonly used

weakly coordinating anion Anions that interact weakly with cations are termed non-coordinating anions, although a more accurate term is weakly coordinating anion. Non-coordinating anions are useful in studying the reactivity of electrophilic cations. They are commonly found ...

References

{{reflist Sulfonic acids Sulfonyl groups Leaving groups Anions Trifluoromethyl compounds

Applications

Triflate salts

See also

References