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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. [ABSTRACT FROM AUTHOR]

Abstract. The five-membered heteroelement cluster THF ·Cl2In(OtBu)3Sn reacts with the sodium stannate [Na(OtBu)3Sn]2 to produce either the new oxo-centered alkoxo cluster ClInO[Sn(OtBu)2]3 ( 1) (in low yield) or the heteroleptic alkoxo cluster Sn(OtBu)3InCl3Na[Sn(OtBu)2]2 ( 2). X-ray diffraction analyses reveal that in compound 1 the polycyclic entity is made of three tin atoms which together with a central oxygen atom form a trigonal, almost planar triangle, perpendicular to which a further indium atom is connected through the oxygen atom. The metal atoms thus are arranged in a Sn3In pyramid, the edges of which are all saturated by bridging tert-butoxy groups. The indium atom has a further chloride ligand. Compound 2 has two trigonal bipyramids as building blocks which are fused together at a six coordinate indium atom. One of the bipyramids is of the type SnO3In with tert-butyl groups on the oxygen atoms, while the other has the composition InCl3Na with chlorine atoms connecting the two metals. The sodium atom in 2 has further contacts to two plus one alkoxide groups which are part of a[Sn(OtBu)2]2 dimer disposing of a Sn2O2 central cycle. The hetero element cluster in 2 thus combines three closed entities and its skeleton SnO3InCl3NaO2Sn2O2 consists of three different metallic and two different non-metallic elements. [ABSTRACT FROM AUTHOR]