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