Date of Award


Document Type


Degree Name

Doctor of Philosophy (PhD)


Two new series of macrocyclic (beta)-ketoamines and several of their metal chelates have been prepared and characterized by infrared spectroscopy, nuclear magnetic resonance spectroscopy, mass spectrometry, and elemental analysis. The two series of (beta)-ketoamines are of type: and. where n = 3,6,7, and 10. They were prepared by reaction of macrocyclic (beta)-diketones with ammonia or ethylenediamine. These compounds were found to exist predominantly in the ketoamine form. A survey was conducted to determine the metal chelation behavior of the macrocyclic (beta)-ketoamines and a few (beta)-ketoamines derived from acetylacetone. The metals and oxocations used in this study were Be(II), Mg(II), Al(III), VO(IV), Cr(III), Mn(II), Fe(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Rh(III), Pd(II), Cd(II), Pt(II), and UO(,2)(VI). For the cyclic (beta)-ketoamines where n = 3 and 6 no chelates were obtained, while for the macrocyclic (beta)-ketoamines where n = 7 and 10 for the acetylacetone derivatives only Cu(II), Ni(II), and Pd(II) chelates could be obtained in high yield. All of the chelates obtained were extractable with chloroform. Also, the fractional sublimation behavior of these chelates was studied. Although most of these chelates were volatile enough to be sublimed in an entrainer fractional sublimation device at reduced pressure, no practical separations could be achieved. In a separate but somewhat related study, the crystal and molecular structures of bis(cyclodecane-1,3-dionato)copper(II) {Cu(CDD)(,2)} and bis(cyclotridecane-1,3-dionato)copper(II) {Cu(CTDD)(,2)} were determined by single crystal x-ray diffraction analysis. In both compounds the copper atom has square planar coordination with the four oxygen atoms. However, there is a greater degree of distortion in the chelate ring of Cu(CDD)(,2) than in that of Cu(CTDD)(,2).