Lightest Member of the Basic Carboxylate Structural Pattern:  [Al₃(μ₃-O)(μ-O₂CCF₃)₆(THF)₃][(Me₃Si)₃CAl(O₂CCF₃)₃]·C₇H₈

Abstract

[Al3(μ3-O)(μ-O2CCF3)6(THF)3][(Me3Si)3CAl(OC(O)CF3)3]·C7H8 is the first characterized μ3-oxo-trinuclear basic carboxylate of aluminum closing the gap of isomorphism with the transition metal analogues. The system is an excellent case study for the electronic structure, approached by DFT-B3LYP calculations. The actual system proves that the oxo-trinuclear pattern is stabilized by the chemical hardness of oxygen donors and by highly symmetric intramolecular packing of the ligands.

Reactions of [(Me3Si)3CAlMe2] with substituted benzoic acids. Isolation of a rare organoalumoxane carboxylate

“…The two AleO distances in the molecule (Al(1)eO(1) 1.827 (3) Al (1)eO (2) 1.817(3) A) are almost equal and are comparable to similar distances found in other organoaluminum carboxylates [26]. The two AleC distances however in the molecule vary somewhat from each other.…”

“…Roesky et al reported the only study involving the use of 1 in organoaluminum carboxylate chemistry, describing the reactions of 1 with CF 3 COOH in a 1:1, 1:2, and 1:3 molar ratios to yield [26]. Of these three products, compound C has been characterized by a single crystal X-ray diffraction study and was found to possess the triangular carboxylate structure with a [M 3 (m 3 -O)] core.…”

“…Especially interesting in this regard would be the reaction of 3,5-dialkyl substituted salicylic acids, which offer a phenolic eOH group, adjacent to eCOOH group, apart from the bulky ( i Pr or t Bu) alkyl substituents on the ring which can offer a kinetic control on the formation of the product. Thus, continuing our interest in main group carboxylate chemistry [23,24], we have probed the reaction of the sterically hindered aluminum alkyl (Me 3 Si) 3 CAlMe 2 $THF (1) [25,26] with a variety of substituted carboxylic acids.…”

A Family of Group 4 Metal Alkoxo Complexes with an M3(μ3‐O) Core Relevant to Ziegler–Natta Catalyst Intermediates

“…[28] This stability prevents any metallic center in such a precatalyst from being activated (for example, by removal of a chlorine atom) and became a polymerization center. It has also been shown that AlMe 3 reacts with [Mg(thffo) 2 ] to form a complex similar to 3 ± 6, namely tetranuclear bimetallic [Al 3 Mg(m 3 -O) (thffo) 3 (Me) 6 ], which has a tetranuclear Al 3 (m 3 -O) core [29] capped with the magnesium moiety.…”

Synthesis, Characterization, and Symmetry Relations of the Crystal Structures of Some Bis(dioxane) Adducts of Group 1 / Group 13 Heterometallic Trifluoroacetates

“…They also described the mixed‐metal trifluoroacetate Cs[In(O 2 CCF 3 ) 4 ], probably composed of alkali metal cations and group 13 metal tetrakis(trifluoroacetato) anions and mentioned the pronounced tendency of group 13 metal trifluoroacetates to coordinate solvent molecules. In general, due to their Lewis‐acidity group 13 metal trifluoroacetates readily form complexes with Lewis bases , . Other relevant carboxylates of group 13 metals include acetates, long chain carboxylates, dicarboxylates,, and there are also examples of mixed‐metal complexes of alkali metal and group 13 metal ions with carboxylato ligands .…”