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structure of the cluster formed from PhC2Li complexed to N,N,N',N'-tetramethyl-1,6-diaminohexane (methylene groups omitted for clarity). Color key: turquoise = Li, blue = N.
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, there is also some evidence for the solubility of ions in liquid ammonia. The ion has a closed shellground state of 1?+ g, making it isoelectronic to a neutral molecule N2, which may afford it some stability.
Analogous acetylides prepared from other metals, particularly transition metals, show covalent character and are invariably associated with their metal centers. This can be seen in their general stability to water (i.e. silver acetylide, copper acetylide) and radically different chemical applications.
Acetylides of the general formula RC?CM (where R = H or alkyl) generally show similar properties to their doubly substituted analogues. In the absence of additional ligands, metal acetylides adopt polymeric structures wherein the acetylide groups are bridging ligands.
Portion of the structure of the polymer copper phenylacetylide (CuC2C6H5).
Illustrative is the sequence shown below, ethyl propiolate is deprotonated by n-butyllithium to give the corresponding acetylide. This acetylide adds to the carbonyl center of cyclopentanone. Hydrolytic workup liberate the alkynyl alcohol.
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).
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^Cataldo, Franco; Casari, Carlo S. (2007). "Synthesis, Structure and Thermal Properties of Copper and Silver Polyynides and Acetylides". Journal of Inorganic and Organometallic Polymers and Materials. 17 (4): 641-651. doi:10.1007/s10904-007-9150-3. ISSN1574-1443.