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Updated: Jul 10, 2026

Spatial Separation of Molecular Conformers and Clusters
Published on: January 9, 2014
Five-coordinate aluminum bromides: synthesis, structure, cation formation, and cleavage of phosphate ester bonds
Amitabha Mitra1, Lauren J Depue, Sean Parkin
1Department of Chemistry, University of Kentucky, Lexington, 40506-0055, USA.
Abstract:
The alkane elimination reaction between Salen((t)Bu)H(2) ligands and diethylaluminum bromide was used to prepare three Salen aluminum bromide compounds salen((t)Bu)AlBr (1) (salen = N,N'-ethylenebis(3,5-di-tert-butylsalicylideneimine)), salpen((t)Bu)AlBr (2) (salpen = N,N'-propylenebis(3,5-di-tert-butylsalicylideneimine)), and salophen((t)Bu)AlBr (3) (salophen = N,N'-o-phenylenenebis(3,5-di-tert-butylsalicylideneimine)). The compounds contain five-coordinate aluminum either in a distorted square pyramidal or a trigonal bipyramidal environment. The bromide group in these compounds could be displaced by triphenylphosphine oxide or triphenyl phosphate to produce the six-coordinate cationic aluminum compounds [salen((t)Bu)Al(Ph(3)PO)(2)]Br (4), [salpen((t)Bu)Al(Ph(3)PO)(2)]Br (5), [salophen((t)Bu)Al(Ph(3)PO)(2)]Br (6), and [salophen((t)Bu)Al[(PhO)(3)PO)](2)]Br (7). All the compounds were characterized by (1)H, (13)C, (27)Al, and (31)P NMR, IR, mass spectrometry, and melting point. Furthermore, compounds 1-3 and 5-7 were structurally characterized by single-crystal X-ray diffraction. Compounds 1-3 dealkylated a series of organophosphates in stoichiometric reactions by breaking the ester C-O bond. Also, they were catalytic in the dealkylation reaction between trimethyl phosphate and added boron tribromide.
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