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Complexes of transition metal ions with naturally occurring ligands Shuter, Edward M.

Abstract

Attempts to prepare tris(ligand)metal complexes of technetium in intermediate oxidation states with potentially bidentate oxazoline- and thiazoline-containing ligands were unsuccessful; when pertechnetate was reduced in the presence of excess ligand, TcO₂ xH₂O was produced. Instead, by reaction with pre-formed metal-oxo cores, a series of oxotechnetium(V) and oxorhenium(V) complexes of the formula MOXL₂(M = Re, X = Br; M = Tc, X = CI), and HL = 2-(2'-hydro xyphenyl)-2-oxazoline (Hoz), 2-(2'-hydroxy-3-methylphenyl)-2-oxazoline (Hmoz), 2-(2' -hydroxyphenyl)-2-thiazoline (Hthoz), and 2-(2' -hydroxyphenyl)-2-benzoxazole (Hhbo) have been prepared. These compounds have been characterized by a variety of techniques, including single crystal X-ray diffraction for two of the complexes, TcOCl(thoz)₂ and ReOBr(oz)₂. In the two complexes, the geometry around the metals is distorted octahedral with the halide ligands in each bound cis, and one phenolate oxygen from one ligand in each bound trans to the metal-oxo linkage. In ReOBr(oz)₂ , the two oxazoline nitrogens are coordinated trans to one another; in TcOCl(thoz)₂, the two thiazoline nitrogens are found cis to one another. In studies of potentially insulin mimetic compounds analogous to bis(maltolato)oxovanadium(IV), the complexes bis(maltolato)oxo(pyridine)vanadium(IV) (VO(ma)₂(py)), oxobis(picolinato)vanadium(IV) monohydrate, (VO(pic)₂(H₂O)), ammonium dioxobis(picolinato)vanadate(V) dihydrate, (NH₄[VO₂(pic)₂]-2H₂O), and bis(maltolato)- dioxomolybdenum(VI), (MoO₂(ma)₂), have been prepared and characterized by elemental analysis, infrared spectroscopy, and mass spectrometry. In addition, the ¹H NMR of the diamagnetic MoO₂(ma)₂ was obtained. Bis(maltolato)methoxyoxovanadium(V), (VO(ma)₂(OMe)), was synthesized and was characterized by ¹H and ⁵¹V NMR infrared spectroscopy, and mass spectromerty. 2-hydroxyethoxybis(maltolato)oxovanadium(V), VO(ma)₂(OCH₂CH₂OH), was characterized by ⁵¹V NMR. X-ray structures were obtained for NH₄[VO₂(pic)₂], VO(ma)₂(OCH₂CH₂OH), and MoO₂(ma)₂.

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