Abstract: 2, 4-Hexadiyne can readily be metalated by n-butyllithium-TMEDA complex at room temperature to give the trilithiated compound MeCSLi3. Reaction of MeC5Li3 with organic and organometallic derivatizing agents yields a variety of isomeric products. Allenynes are the major products, although cumulenes and diacetylenes are also formed. Derivatization with trimethylchlorosilane yields small amounts of a hexasilylated product, ...