Gallium and Indium Alkoxides with Hydride, Cyclopentadienediide and Copper(I) tert‐Butoxide as further Components

Abstract

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.

Molecular Main Group Metal Hydrides

“…Systems containing anionic (X-type) oxygen-based ligands, such as alkoxides, show an increased tendency to adopt oligomeric structures reflecting, at least in part, the smaller steric profile of OR substituents (cf., NR 2 ). Synthetically, Ga–O bonds in systems of this type tend to be accessed in facile fashion via protonolysis reactions of existing Ga–H linkages with alcohols and related OH-containing reagents. − Insertion of a carbonyl function into an existing Ga–H bond offers an alternative approach, for example, in the formation of O i Pr substituents from acetone . Regarding protonolysis, Veith, has reported the synthesis of a range of cyclic siloxygallanes derived from the reactions of [H 2 Ga­(μ-O t Bu) 2 GaH 2 ] ( 672 ) with silanols .…”

“…860−863 Insertion of a carbonyl function into an existing Ga−H bond offers an alternative approach, for example, in the formation of O i Pr substituents from acetone. 864 Regarding protonolysis, Veith, (674), which retains two of the terminal Ga−H bonds associated with each gallium center from the precursor, and features t BuO ligands bridging both GaMg and MgMg pairs (Figure 52). 863 In similar fashion, β-ketoiminate ligands can be employed for the stabilization of monomeric gallium hydride complexes by exploiting reactions between Me 3 N•GaH 3 and the corresponding protio ligands.…”