Lithium-mediated ring opening of 1,4-dioxane and structural characterization of a Li12O12 truncated octahedron

The equimolar reaction of tBuLi with 4-Cl-2,6-Me2-C6H2OH (ArOH) in 1,4-dioxane led to the unexpected formation of the mixed-anion, 1D polymer [(ArO)2(RO)4Li6 · (diox)]∞, 1 (where RO = H2Cdouble bond; length as m-dashC(H)OCH2CH2O−). Incorporation of the alkoxy vinyl ether is due to cleavage of 1,4-dioxane by tBuLi. Compound 1 can also be prepared rationally by the reaction of nBuLi with ethylene glycol vinyl ether and ArOH in 1,4-dioxane solution. Direct lithiation of ethylene glycol vinyl ether results in the formation of the alkoxide [ROLi]12, 2. The crystal structure of 2 reveals an unusual truncated octahedral arrangement in the solid state, where each metal is chelated by a vinyl ether subunit.