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The present work entails the synthesis and first structural characterization of complexes possessing a single Al−O−Si linkage. These are of the formula LAlOSiPh3 (L = Salen(tBu) (N,N‘-ethylenebis(3, 5-di-tert-butylsalicylideneimine)) (11); Salpen(tBu) N,N‘-propylenebis(3,5-di-tert-butylsalicylideneimine)) (12); Salophen(tBu) (N,N‘-phenylenebis(3,5-di-tert-butylsalicylideneimine)) (13); and Salomphen(tBu) (N,N‘-(3,4-dimethylphenylene)bis(3,5-di-tert-butylsalicylideneimine)) (14). They are formed by combining the novel five-coordinate aluminum alkyl starting materials L(tBu)AlR (where L = Salen(tBu), R = Me (1), Et (2), iBu (3); Salpen(tBu), R = Me (4), Salophen(tBu) R = Me (5), Et (6), iBu (7); and Salomphen, R = Me (8), Et (9), iBu (10)) with Ph3SiOH in toluene. All of the compounds were characterized spectroscopically and, in the case of 1, 10, 11, 12, and 13, by X-ray crystallography.

Herein are described the synthesis and characterization of the complexes of formula LAlR (where R = Cl and L = Salen (1), SalenCl (2), Acen (3) and where R = Me and L = Salen (4), SalenCl (5), Acen (6); Salen = N,N'-ethylenebis((2-hydroxyphenyl)methylimine), SalenCl = N,N'-ethylenebis((2-hydroxy-5-chlorophenyl)methylimine), Acen = N,N'-ethylenebis((2-hydroxyphenyl)-1-ethylimine)). The LAlCl derivatives dissolve in water and MeOH to yield the cationic complexes [LAl(H(2)O)(2)](+)Cl(-) (L = Salen (7), SalenCl (8), Acen (9)) and [LAl(MeOH)(2)](+)Cl(-) (L = Salen (10), SalenCl (11), Acen (12)), respectively. An alternative preparation of the cationic species involves the reaction of the LAlCl derivative with NaBPh(4). This leads to complexes of formula [LAl(MeOH)(2)](+)BPh(4)(-) (L = Salen (13), SalenCl (14), Acen (15)). Complexes 4-6 can be reacted with either MeOH or 4-chloro-3,5-dimethylphenol (Ph') to form complexes of general formula LAlOR (R = Me, L = Salen (16), SalenCl (17), Acen (18); R = Ph', L = Salen (19), SalenCl (20), Acen (21)). All of the compounds were characterized by IR, melting points, elemental analyses, and, when soluble, NMR. Additionally, the crystal structures of 7, 13, 15, and 18 were obtained.

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A new series of aluminum alkoxide molecules of formula [Al{(µ-OEt) 2 AlR 2 } 3 ], where R ) Me (1), Et (2), i Bu (3), and [Al{(µ-OEt) 2 GaR 2 } 3 ], where R ) Me (4) and Et (5), have been synthesized and fully characterized. In pure form 1, 2, and 4 are crystalline solids. However, in the presence of a small amount of solvent or impurity all of the compounds exist as oils. They were characterized by 1 H NMR, IR, elemental analysis, mp, and single-crystal X-ray diffractometry for compounds 1, 2, and 4.