In chemistry, an acetylide is a compound that can be viewed as the result of replacing one or both hydrogen atoms of acetylene (ethyne) HC\tCH by metallic or other cations. Calcium carbide is an important industrial compound, which has long been used to produce acetylene for welding and illumination. It is also a major precursor to vinyl chloride. Other acetylides are reagents in organic synthesis.

Nomenclature

The term acetylide is used loosely, for any compound obtained in the same way from an acetylene derivative RC\tCH, where R is some organic side chain. The nomenclature of acetylides can be ambiguous with regards to the distinction between compounds of the type MC2R and M2C2. When both hydrogens of acetylene are replaced by metals, the compound can be calledcarbide, e.g. calcium carbide Ca(2+)C\tC(2-). When only one hydrogen atom is replaced, the anion may be called hydrogen acetylide or the prefix mono- may be attached to the metal, as in monosodium acetylide Na+HC\tC-. An acetylide may be a salt (ionic compound) containing the anion C\tC(2-), HC\tC-, or RC\tC-, as in sodium acetylide [Na+]2C\tC(2-) or cobalt acetylide Co(2+)C\tC(2-). Other acetylides have the metal bound to the carbon atom(s) by covalent bonds, being therefore coordination or organometallic compounds.

Ionic acetylides

Alkali metal and alkaline earth metal acetylides of the general formula MC≡CM are salt-like Zintl phase compounds, containing ions. Evidence for this ionic character can be seen in the ready hydrolysis of these compounds to form acetylene and metal oxides, and by solubility in liquid ammonia with solvated ions. The ion has a closed shell ground state of 1Σ+ g, making it isoelectronic to a neutral molecule N2, which may afford it some gas-phase stability.

Organometallic acetylides

Some acetylides, particularly of transition metals, show evidences of covalent character, e. g. for being neither dissolved nor decomposed by water and by radically different chemical reactions. That seems to be the case of silver acetylide and copper acetylide, for example. In the absence of additional ligands, metal acetylides adopt polymeric structures wherein the acetylide groups are bridging ligands.

Preparation

Of the type MC2R

Acetylene and terminal alkynes are weak acids: Monopotassium and monosodium acetylide can be prepared by reacting acetylene with bases like sodium amide) or the elemental metals, often at room temperature and atmospheric pressure. Copper(I) acetylide can be prepared by passing acetylene through an aqueous solution of copper(I) chloride because of a low solubility equilibrium. Similarly, silver acetylides can be obtained from silver nitrate. In organic synthesis, acetylides are usually prepared by treating acetylene and alkynes with organometallic or inorganic Classically, liquid ammonia was used for deprotonations, but ethers are now more commonly used. Lithium amide, LiHMDS, or organolithium reagents, such as butyllithium (BuLi), are frequently used to form lithium acetylides:

Of the type M2C2 and CaC2

Calcium carbide is prepared industrially by heating carbon with lime (calcium oxide) at approximately 2,000 °C. A similar process can be used to produce lithium carbide. Dilithium acetylide, Li2C2, competes with the preparation of the monolithium derivative LiC2H.

Reactions

Ionic acetylides are typically decomposed by water with evolution of acetylene: Acetylides of the type RC2M are widely used in alkynylations in organic chemistry. They are nucleophiles that add to a variety of electrophilic and unsaturated substrates. A classic application is the Favorskii reaction, such as in the sequence shown below. Here ethyl propiolate is deprotonated by n-butyllithium to give the corresponding lithium acetylide. This acetylide adds to the carbonyl center of cyclopentanone. Hydrolysis liberates the alkynyl alcohol. The dimerization of acetylene to vinylacetylene proceeds by insertion of acetylene into a copper(I) acetylide complex.

Coupling reactions

Acetylides are sometimes used as intermediates in coupling reactions. Examples include Sonogashira coupling, Cadiot-Chodkiewicz coupling, Glaser coupling and Eglinton coupling.

Hazards

Some acetylides are notoriously explosive. Formation of acetylides poses a risk in handling of gaseous acetylene in presence of metals such as mercury, silver or copper, or alloys with their high content (brass, bronze, silver solder).