Synthesis and structural studies of chiral indium(III) complexes supported by tridentate diaminophenol ligands.

Indium(III) dimethyl, dihalide, and alkoxy-bridged complexes bearing a chiral diaminophenoxy tridentate ligand [NN(H)O](-) were synthesized. The dimethyl complex (NN(H)O)InMe(2) (1) was unreactive toward ethanol and 2-propanol and only partially reactive toward the more acidic phenol. The dihalide complexes (NN(H)O)InX(2) (X = Cl (3), Br (4), I (5)) reacted with NaOEt to form robust alkoxy-bridged complexes with the formula {[(NN(H)O)InX](2)(mu-X)(mu-OEt)} (X = Cl (6), Br (7), I (8)). The reaction of the alkoxy-bridged complexes with water produced hydroxy-bridged dinuclear indium compounds. The hydroxy-bridged complex bearing a chloride ligand [(NN(H)O)InCl(mu-OH)](2) (9) was significantly more reactive toward dissociation and formation of a pyridine adduct than the iodo analogue [(NN(H)O)InI(mu-OH)](2) (10). All compounds were fully characterized in solution by NMR spectroscopy and in the solid state by single-crystal X-ray diffraction. In addition, DFT calculations were used to help explain the reactivity trends observed.