Alcoholysis of Al₂(OtBu)₆ – Synthesis and Crystal Structure of Al₉O₃(OEt)₂₁

Abstract

When Al2(OtBu)6 is treated with ethanol, Al9O3(OEt)21 (1) is obtained, which is a missing link in the series of polynuclear aluminum alkoxides. Alcoholysis of Al2(OtBu)6 in 2‐propanol yields the well‐known homoleptic compound Al4(OiPr)12 (2). As recently published, similar reactions with Fe2(OtBu)6 gave different structures. However, there are recurring structural patterns from alkoxide chemistry found. For a deeper understanding of this hardly predictable chemistry, compounds have to be correlated by such common structural motifs. We briefly report the syntheses of 1 and 2 and the crystal structure of 1. In addition, we provide an improved synthetic procedure for the preparation of the precursor Al2(OtBu)6. The structure of the new compound 1 is comprehensively compared to related structures from literature.

Designable Aluminum Molecular Rings: Ring Expansion and Ligand Functionalization

“…To create crystalline Al III -based materials,the controllable hydrolysis of Al III sources into measurable crystals is ab ig challenge.C ompared to the 150-year-old chemistry of hydrolysis of inorganic Al III salts, [7][8][9][10][11][12] the hydrolysis of organoaluminium compounds is relatively new. [13][14][15][16][17][18][19] More importantly,o rganoaluminium with highly tailorable shape,c omposition, and surface properties represents an excellent platform for significant atomistic understanding.H owever, the fast hydrolysis of aluminum salts/alkoxides usually results in the formation of ametal oxide/hydroxide.Inthis regard, it is important to slow down its hydrolysis process to promote crystallization and simultaneously enable condensation occurs.R ecently,w eh ave applied organic ligands to delay the hydrolysis process of Ti IV ions through coordination interactions (denoted as coordination delayed hydrolysis (CDH)). [20][21][22][23][24] Therefore,w eb elieve the strategy can be used to understand the hydrolysis and condensation of Al III precursors,w hich remained relatively unexplored before.…”

The crystal structure of the decaaluminum alkoxide cluster Al10O4(OH)8 L 14 (L = 1,1,1,3,3,3-hexafluoropropan-2-olate)

“…A pentanuclear, Al 5 O(Oi-Bu) 13 , and octanuclear structure, Al 8 O 2 (OH) 2 (OiBu) 18 (iBu = iso-butyl), was determined in 2002 (Abrahams et al, 2002). In 2018, the structure of a nonanuclear structure, Al 9 O 3 (OEt) 21 , was reported (Nachtigall et al 2018). In 1987, the decanuclear compound, Al 10 O 4 (OEt) 22 , was reported (Yanovsky et al, 1987).…”

“…In larger aggregates, in the case of Al 8 O 2 (OH) 2 (OiBu) 18 (Abrahams et al, 2002), these building blocks are linked by two -OH units. For Al 9 O 3 (OEt) 21 (Nachtigall et al 2018), these building blocks are linked by two moieties. The first is a 3 (O) group linking the two halves as well as the ninth Al atom.…”

Synthesis, Structures and Optical Limiting of Catecholato‐Based Aluminum Oxo Clusters

“…[7][8][9][10] The hydrolysis of organoaluminum compounds has attracted attention over the last four decades. [11][12][13][14][15][16] Above all, organoaluminium provides a great platform for effective atomistic understanding due to its customizable shape and composition. Based on our previous study on metal oxo clusters, [17][18][19] we synthesized a series of aluminum oxo clusters (AlOCs).…”

“…They synthesized new aluminum hydroxide clusters from an aqueous solution and investigated the adsorption properties of Keggin‐type polyaluminum species [7–10] . The hydrolysis of organoaluminum compounds has attracted attention over the last four decades [11–16] . Above all, organoaluminium provides a great platform for effective atomistic understanding due to its customizable shape and composition.…”