Group 13 Cation Formation with a Potentially Tridentate Ligand

Abstract

A potentially tridentate ligand, Phensal(tBu)H 3 , was prepared by the condensation of 1 equiv of phenylenediamine with 3,5-di-tert-butylsalicylaldehyde. When 1 equiv of this new ligand is added to AlMe 3 , [[Phensal(tBu)HAlMe]] 2 (1) results. In contrast, this reaction with GaMe 3 produces [Phensal(tBu)H 2 ]GaMe 2 (2). When 1 or 2 equiv of Phensal(tBu)H 3 is combined with Et 2 AlCl, the complex [Phensal(tBu)] 2 AlCl (3) forms. However the same reaction with Me 2 GaCl leads to [Phensal(tBu)H 2 ]Ga(Me)Cl (4). A cationic complex, {[Phensal(tBu)] 2 Al} + Cl -(5), is formed when 3 is dissolved in MeOH. The MeOH apparently mediates the formation of the cation but does not coordinate the cationic metal. When the solvent is removed, 5 reverts back to neutral 3. When 3 is combined with GaCl 3 in toluene, another cationic complex, {[Phensal(tBu)H 2 ] 2 Al} + GaCl 4 -(6), is formed. In a similar manner, {[Phensal(tBu)H 2 ] 2 Al} + Me 2 AlCl 2 -(7) is formed by adding Me 2 AlCl to 3. The compounds were characterized by mp, elemental analyses, IR, 1 H and 27 Al NMR, and in the case of 2, 5, and 6 single-crystal X-ray analysis.Supporting Information Available: Crystallographic data for compounds 2, 5, and 6, which includes full tables of bond lengths and angles, full atom-labeled ORTEP views, and unit cell views. This material is available free of charge via the Internet at http://pubs.acs.org. Observed and calculated structure factor tables are available upon request. This data may also be obtained at the Cambridge Crystallographic Database (CCDC 139436, 139437, 139438).

ZnII–Salphen Complexes as Versatile Building Blocks for the Construction of Supramolecular Box Assemblies

“…[9] Under suitable reaction conditions, that is, in the presence of zinc(ii) acetate and one equivalent of an aldehyde precursor, we did not observe any scrambling, and product 9 was also isolated simply by filtration.…”

Supramolecular zinc(II)salphen motifs: Reversible dimerization and templated dimeric structures

“…Compound 3 was prepared using the literature method [9] and was used as starting material for the preparation of 4. All compounds were isolated as pure powders by a simple filtration step [7a].…”

“…MS measurements were performed on a Shimadzu LCMS-2010A spectrometer with atmospheric pressure chemical ionization. Complexes 2-4 were prepared as reported previously [7a], while mono-imine 1 was prepared according to the literature procedure [9].…”

Fine Tuning of the Oxidation Locus, and Electron Transfer, in Nickel Complexes of Pro‐Radical Ligands

“…2-Amino-1-(3,5-di-tert-butyl-2-hydroxybenzimino)benzene: This precursor for H 3 L 2 was prepared according to the procedure of Atwood et al [26] 2-(3,5-Di-tert-butyl-2-hydroxybenzamido)-1-(3,5-di-tert-butyl-2-hydroxybenzimino)benzene (H 3 L 2 ): As described below for the synthesis of ligand H 4 L 3 , 3,5-di-tert-butylsalicyl chloride (410 mg, 1.5 mmol) in dichloromethane (20 mL) was coupled with 2-amino-1-(3,5-di-tert-butyl-2-hydroxybenzimino)benzene (500 mg, 1.5 mmol) in dichloromethane (30 mL) and worked up in the same way. The raw product was purified by column chromatography over silica gel (100 g) with pentane/dichloromethane (1:1) : o-Phenylenediamine (220 mg, 2 mmol) was dissolved in dry dichloromethane (20 mL) and the solution was cooled to À40 8C.…”