Open Access

The synthesis of 4,4′‐di‐tert‐butyl‐4H,4′H‐2,2′‐spirobi[benzo[d][1,3,2]dioxagermine] (1) and 4,4′,8,8′‐tetra‐tert‐butyl‐4H,4′H‐2,2′‐spirobi[benzo[d][1,3,2]dioxagermine] (2) being the first representatives of spirocyclic germanium salicyl alcoholates is reported. The reaction of these compounds with potassium fluoride in the presence of 18‐crown‐6 gives the alkoxido fluorido germanates [K(CH2CH2O‐)6][GeF{OC6H4(CHtBuO)‐2}2] (3) and [K(CH2CH2O–)6][GeF{OC6H3(CHtBuO)‐2‐tBu‐6}2] (4). All compounds are characterized including single crystal X‐ray diffraction analysis, nuclear magnetic resonance spectroscopy [1H, 13C{1H}, 1H–13C{1H} heteronuclear single quantum coherence, and 19F (3 and 4)], infrared spectroscopy, and thermal analyzes. Single crystal X‐ray diffraction analyzes unveil a change of chirality in the salicyl alcoholate moieties of 3 with respect to the dominant (≈66%) stereoisomer of 1 upon crystallization as a result of fluoride‐induced ligand exchange equilibria. Reactivity studies of the compounds 1 and 2 are discussed in comparison with structurally related silicon‐based twin monomers.