Reactions of metallic Ba with benzofuranol (dbbfoH) or diethylene glycol give homoleptic and homonuclear complexes Ba(dbbfo)(2)-(dbbfoH)(2)center dot 3dbbfoH and Ba{O(CH2CH2O)(2)}{O(CH2CH2OH)(2)}(2) (60-89%). Both compounds and formerly described Ba{O(CH2CH2O)(2)-Me}(2) react with Al(CH3)(3) to yield trinuclear heterobimetallic low-coordinated barium compounds with structure and geometry depending on the reaction stoichiometry and crystallization procedure.