The syntheses of the ionic compounds [Li+.2 dioxane (2,6-iPr(2)C(6)H(3)N(SiMe3)Al(CdropCSiMe(3))(3))(-)].0.75 dioxane (1), [(Li+)(2).(dioxane)(7)](0.5) [2,6-iPr(2)C(6)H(3)N(SiMe3)Ga(CdropCSiMe(3))(3)(-)] . 1.5 dioxane (2), and [(Li+)(2).(dioxane)(7)]0,5 [2,6-Pr2C6H3N-(SiMe3)ln(C=CSiMe3)(3)(-)].1.5 dioxane (3) by the reaction of the corresponding organo metal chloride with LiCdrop CSiMe3 are reported. The neutral ethynyl compounds Br-Al(C=CtBu)(2).2 THF (4), Cl-Ga(CdropCtBu)(2).THF (5), Cl-ln(CdropCtBu)(2).2 THF (6), Al(CdropCtBu)(3).C{N(Me)CMe}(2) (7), Ga(CdropCtBu)(3).dioxane (8), and ln(CdropCtBu)(3).NEt3 (9) have been obtained in good yields from the reaction of AlBr3, GaCl3, and lnCl(3) with LiCdropCtBu in the presence of a Lewis base. Compound 7 is the first heterocyclic carbene substituted ethynyl derivative. Aluminum and gallium compounds with three terminal ethynyl groups Al(CdropCPh)(3).NMe3 (10) and Ga(CdropCPh)(3).NMe3 (11) have been prepared by the reaction of AIH(3)-NMe3 or GaH3.NMe3 with three equivalents of phenylethyne. All the above-mentioned compounds have been structurally studied. In compound 1 the lithium ion is coordinated to the three terminal ethynyl groups, whereas in compounds 2 and 3 the lithium is coordinated to the solvent (dioxane). Compound 8 crystallizes as a coordination polymer with dioxane molecules bridging the individual gallium units.