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Permanent link (DOI): https://doi.org/10.7939/R3HT0S

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Synthesis of bicyclic and bimetallic titanacyclobutenes Open Access

Descriptions

Other title
Subject/Keyword
macrocyclization
eta-3-propargyl
radical
titanacyclobutene
Type of item
Thesis
Degree grantor
University of Alberta
Author or creator
Quesnel, Jeffrey Scott
Supervisor and department
Stryker, Jeffrey M. (Chemistry)
Examining committee member and department
Semagina, Natalia (Chemicals and Materials Engineering)
Clive, Derrick L. J. (Chemistry)
Department
Department of Chemistry
Specialization

Date accepted
2009-10-02T16:29:17Z
Graduation date
2009-11
Degree
Master of Science
Degree level
Master's
Abstract
In an attempt to expand the scope of titanacyclobutenes, malonate-derived α,ω-alkylpropargyl dibromides and α,ω-bis(bromopropargyl) malonates were prepared and examined for their reactivity with titanocene reagents. Unfortunately, all of the α,ω-alkylpropargyl dibromomalonates failed, presumably from chelation of the carbonyl oxygen followed by radical or nucleophilic attack. The α,ω-bis(bromopropargyl) malonate substrates allowed the successful synthesis of ester-functionalized allenyl or alkynyl-substituted bicyclic titanacyclobutene complexes. Allenyl-substitution is favoured when the being formed ring is small. When ring strain is minimal, cycloalkynes are obtained. An impressive example of a twelve-membered macrobicyclic titanacyclobutene was achieved, supported by extensive NMR spectroscopy and X-ray crystallography. η3-Propargyltitanium(III) complexes were synthesized and displayed equilibrium behaviour between the monomeric propargyl and dimeric di(titanacyclobutene) forms. Both steric and electronic effects are believed to be contributing factors for dimerization. Bimetallic titanacyclobutenes are obtained from the reaction of an epoxide and titanocene monochloride in the presence of a η3-propargyltitanium(III) complex.
Language
English
DOI
doi:10.7939/R3HT0S
Rights
Permission is hereby granted to the University of Alberta Libraries to reproduce single copies of this thesis and to lend or sell such copies for private, scholarly or scientific research purposes only. Where the thesis is converted to, or otherwise made available in digital form, the University of Alberta will advise potential users of the thesis of these terms. The author reserves all other publication and other rights in association with the copyright in the thesis and, except as herein before provided, neither the thesis nor any substantial portion thereof may be printed or otherwise reproduced in any material form whatsoever without the author's prior written permission.
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