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.
Acosta-Ramírez
Alberto
A
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, BC, Canada.
Douglas
Amy F
AF
Yu
Insun
I
Patrick
Brian O
BO
Diaconescu
Paula L
PL
Mehrkhodavandi
Parisa
P
D000627:Aminophenols / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007204:Indium / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism
D000627:Aminophenols; D008024:Ligands; D009942:Organometallic Compounds; D007204:Indium