Date of Award
Doctor of Philosophy
This thesis describes a preparative route to chiral fluorinated amino-alcohol ligands via the Schiff base template condensation reaction. The synthetic route consists of three main steps; (1) template condensation of a primary amine with 5,5,5-trifluoro-5-hydroxy-4-(trifluoromethyl)-2-pentanone, HFDA, in the presence of Cu('2+) ions, (2) hydride reduction of the resulting Schiff base copper(II) complex, and (3) isolation of the optically active ligand. Two new types of ligands are prepared; bidentate imino- and amino-alcohol ligands derived from monofunctional amines, R-NH(,2), and tridentate imino- and amino-diol ligands derived from bifunctional aminoalcohols, NH(,2)-OH.;The bidentate ligands are uninegative and form CuL(,2) complexes with a square planar trans geometry. The type of complex which forms with the tridentate ligands depends upon the length of the carbon chain in the original aminoalcohol.;The hydride reduction of chiral copper(II) Schiff base complexes produces a mixture of diastereomers. A scheme of (1) isolating one diastereomer by fractional crystallization; (2) preparing the copper(II) complex; and (3) recording the circular dichroism spectrum for these complexes allows us to assign an absolute configuration. The absolute configuration and geometry of Cu(O-C*-NH-Men*)(,2) is determined by X-ray crystallography. ('1)H and ('19)F n.m.r. investigations designed to determine the diastereomeric product distribution and predictions of the stereochemistry are discussed.;The studies of magnetic exchange interactions for different series of alkoxy-bridged copper(II) complexes is described. Differing degrees of antiferromagnetic exchange are observed depending upon the size of the chelate ring. The phenomenon is investigated in the study of two analogous series of complexes with an R-group substituted on the bridging chelate ring. The variations in magnetic exchange are discussed in terms of different structural parameters involved in the Cu(,2)O(,2) bridging core.
Loeb, Stephen Joseph, "Synthetic And Structural Studies On Chiral Fluorinated Imino- And Amino-alcohols And Their Copper(ii) Complexes" (1982). Digitized Theses. 1212.