Gallium hydride stabilized by the base quinonuclidine reacts with acetone under addition of the Ga‐H function to the carbon–oxygen double bond yielding (HGa)5(OiPr)8O (1) as isolable compound. (HGa)5(OiPr)8O may be formally split in to four entities of HGa(OiPr)2 and one entity HGaO. The inner atomic skeleton of 1 is a novel Ga5O9 heterocluster with gallium atoms occupying the corners of a distorted trigonal bi‐pyramid, an oxygen atom in the center and the remaining alcoholate oxygen atoms bridging eight of the nine edges of the bi‐pyramid (X‐ray diffraction analysis). Potassium indium alkoxide KIn(OtBu)4 has been used to synthesize several new compounds like In4(OtBu)8(C5H4)2 (2), (py)2CuIn(OtBu)4 (3), and [CuIn(OtBu)4]2 (4) by reaction with TiCl2cp2 (2) and CuCl (3, 4). All compounds were characterized by spectroscopic means and by X‐ray structure analyses revealing novel polycyclic structures.

The cover picture shows the structure of the hydrido galliumoxide‐alkoxide (H‐Ga)5(O‐iPr)8(O) emphasizing the inner Ga5O9 polycyclic skeleton (R=iso‐Propyl). Such Lewis‐acid/base agglomerates, based on metal alkoxides, can be used to combine not only hydride and oxide in a molecular compound, but also indium and C5H42– as shown for In4(OtBu)8(C5H4)2, or indium and copper as found in (py)2CuIn(OtBu)4 or in [CuIn(OtBu)4]2. Such molecules can be used as precursors for materials synthesis. More details can be found in the article by Michael Veith, Daniela Summa, Uwe Annel, and Volker Huch on page 1272.