Synthesis of gamma-diimine and iminoisoindoline ligands for applications in palladium and aluminum coordination chemistry and catalysis

This work began with the synthesis and full characterization of a novel gamma-diimine ligand, (2,6-iPr2C6H3N=CH) 2C6H4, from the reaction of o-phthaladehyde and the bulky aniline, 2,6-diisopropylaniline. It was observed that any di-ortho-substituted aniline with less bulky groups than isopropyl groups resulted in formation of the corresponding iminoisoindolines. Reaction of the gamma-diimine ligand with PdCl2 did not result in a seven-membered coordination complex, but in non-palladacyclic complex [(gamma-diimine)PdCl(micro-Cl)]2. Whereas reaction with Pd(OAc) 2 gave an S-shaped five-membered trinuclear palladacyclic complex, {1,2-(2,6- iPr2-C6H3N=CH)2-C 6H3]Pd(micro-OAc)2}2Pd. These complexes were found to be active precatalysts for Heck and Suzuki coupling reactions giving TONs of up to 104 and 86 for aryl bromides and aryl chlorides, respectively.;Also illustrated in this thesis is the synthesis and characterization of a series of air- and moisture-stable iminoisoindoline-based palladacyclic compounds of the general formula, [(iminoisoindoline)Pd{micro-OAc}] 2. These six-membered palladacyclic complexes were obtained through a simple two-step protocol as analytically pure solids. Phosphine-ligated mononuclear palladacycles of the general formula, [Pd(iminoisoindoline)X(PR 3)], (X= OAc or Cl, R = Ph or Cy), are also described. Dinuclear palladacycles were also found to be active for the Heck and Suzuki C-C coupling reactions. TONs of up to 106, 105 and 60 were observed for coupling of iodobenzene, p-acetylbromobenzene and p-chlorobenzaldehyde, respectively with butylacrylate in the Heck coupling reaction.;In addition, the syntheses and characterization of mixed iminoisoindolines, where the two aryl groups of the ligand contain different substituents, and their corresponding six-membered imine-based [CN] palladacycles of the general formula [(N,N'-diaryliminoisoindoline)Pd{micro-OAc}]2 are described.;All complexes were characterized by standard spectral methods such as mass spectrometry, X-ray crystallography, elemental analysis, 1H NMR, 13C NMR and IR spectroscopies.;On the other hand, a series of neutral and cationic seven-membered aluminum coordination complexes were obtained from the reaction of gamma-diimine with a variety of aluminum species (AlMe3, AlMe2Cl, AlMeCl2 and AlCl3). The synthesis and characterization of these complexes are exemplified.