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Neutral triple-decker complexes of the heavy alkaline earth metals and ytterbium with tetraiso-propylcyclopentadienide anions as terminal ligands and a cyclooctatetraene dianion as a middle deck have been synthesized from tetraisopropylcyclopentadienyl metal halide precursors and disodium cyclooctatetraenide. The pentaisopropylcyclopentadienyl analogue [{(C5iPr5)Yb}2(C8H8)] was prepared from ytterbium metal, cyclooctatetraene, and the free pentaisopropylcyclopentadienyl radical. X-ray crystal structure determinations for the barium and the calcium derivative show an almost linear arrangement of ring centers and metal atoms in both cases with metal-ring center distances of 2.33 Å (Ca-Cp), 1.99/1.98 Å (Ca-COT) and 2.71 Å (Ba-Cp), 2.40 Å (Ba-COT). The geometrical features of these molecules could be modeled quite accurately with density functional calculations. With potassium cyclononatetraenide, sparingly soluble bis(cyclononatetraenyl)barium could be prepared and characterized by 1H and 13C NMR spectroscopy, mass spectrometry, and elemental analysis. Cyclononatetraenyl(tetraisopropylcyclopentadienyl)- barium was obtained from ((C5HiPr4)Bal(THF)2]2 and KC9H9 as a 1:1 mixture with octaisopropylbarocene. Density functional calculations predict sandwich structures with parallel rings and a 2.37 Å Ba-ring distance for [Ba(C9H9)2] and a 174° bending with metal-ring distances of 2.72 Å (Ba-Cp) and 2.35 Å (Ba-CNT) for [(C5HiPr4)Ba(C9H9)]. All alkaline earth sandwich and triple-decker complexes mentioned above have been heated to 250 °C without decomposition and have been sublimed in oil pump vacuum. [ABSTRACT FROM AUTHOR]