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UBC Theses and Dissertations
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.
Item Metadata
Title |
Complexes of transition metal ions with naturally occurring ligands
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Creator | |
Publisher |
University of British Columbia
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Date Issued |
1995
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Description |
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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Extent |
2254679 bytes
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Genre | |
Type | |
File Format |
application/pdf
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Language |
eng
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Date Available |
2009-01-23
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Provider |
Vancouver : University of British Columbia Library
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Rights |
For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.
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DOI |
10.14288/1.0059532
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URI | |
Degree | |
Program | |
Affiliation | |
Degree Grantor |
University of British Columbia
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Graduation Date |
1995-11
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Campus | |
Scholarly Level |
Graduate
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Aggregated Source Repository |
DSpace
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For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.