[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.
By using Pearson's HSAB principle [Ag(Toluene)3]+ [{((SiMe3)3C)2Al2F5}2Li]- (2) has been synthesized from the reaction of [(SiMe3)3CAlF2]3 (1) with
AgF and LiCl. Reaction of 1 with AgF2 and NH4F
affords [AlF2(THF)4]+ [{(SiMe3)3C}2Al2F5]- (3) and [NH4]+
[(SiMe3)3CAlF3]- (4) , respectively. 2 and 3 have been
structurally characterized.
A facile synthesis utilizing tetra-n-butylammonium hydrogen difluoride and Group 13 alkyl compounds leads to the soluble salts 1 - 4. Compound 1 is the smallest difluoro-diorganoaluminate so far characterized. The corresponding gallium and indium derivatives 3 and 4 are not sensitive to moisture.
The synthesis of [K + ‚THF(2,6-iPr 2 C 6 H 3 N-(SiMe 3 )Al(CtCPh) 3 ) -] 2 (1), [Na + ‚THF (2, 4) with the corresponding phenylethynyl alkali metal salt is reported. In compound 1 the potassium (2, sodium) interacts with the CtC bonds of four phenylethynyl groups. A further coordination site of the potassium (sodium) is occupied by a THF molecule. Thus, the cation therein acts as a bridging moiety to form the dimer. In compound 3 each of the lithium cations is 2-fold coordinated by phenylethynyl ligands and two dioxane molecules. One of the dioxane molecules in 3 functions as a bridge forming the dimer. The herein described compounds are the first structurally characterized species having three terminal phenylethynyl groups bound to the aluminum atom.
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