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Titanacyclobutene and Cobalt(II) Phosphinimide Complexes Open Access


Other title
Titanium(IV) Sulfimide
Phosphorane imide
Titanium(IV) Phosphinimide
Cobalt(II) Phosphinimide
Type of item
Degree grantor
University of Alberta
Author or creator
Gauthier, Jeremy M.
Supervisor and department
Stryker, Jeffrey (Chemistry)
Examining committee member and department
Semagina, Natalia (Engineering)
Takats, Josef (Chemistry)
West, Fred (Chemistry)
Hall, Dennis (Chemistry)
McNeil, Stephen (Chemistry, UBC Okanagan)
Department of Chemistry

Date accepted
Graduation date
Doctor of Philosophy
Degree level
This dissertation describes some advances that were made in the field of paramagnetic first-row transition metal complexes. Two independent topics will be discussed. The first topic that will be discussed is the preparation and reactivity of titanacylobutene complexes. Initially, the Stryker group discovered that titanacyclobutenes can be prepared by the SmI2-mediated coupling of propargyl halides, [Cp2TiCl]2, and alkyl halides. We have since improved on this procedure; this involves replacing [Cp2TiCl]2 with titanocene(IV) dichloride, and replacing SmI2 with activated manganese powder. These conditions now give chemists the ability to prepare titanacyclobutenes from reagents that do not have to be kept under an inert atmosphere. The second part of this topic discusses the conversion of titanacyclobutenes into 5-membered α-iminoenamine carbocycles. Iit has been demonstrated that titanacyclobutenes undergo double-insertion reactions with organic isonitriles which form carbocyclic-titanium enediamidate complexes however, successful reaction conditions for obtaining the titanium-free 5-membered carbocycles were unknown. We now report that 5-membered α-iminoenamine carbocycles can be obtained from carbocyclic-titanium enediamidate complexes through protonation, using 2,4,6-collidine hydrochloride. The last part of this topic discusses our attempts to prepare titanacyclobutenes from titanium(IV) precursors which contain alternative ligands than cyclopentadienyl ligands. Trialkyl-phosphoranimide and diphenyl-sulfimide ligands are ideal candidates for this chemistry, because the imide nitrogen of both ligands acts as a six-electron donor to the titanium(IV) center and the alkyl or aryl substituents provide suitable steric shielding to the metal center. This section discusses both the preparation and reactivity of three precursors: ((t-bu)3PN)2TiCl2, Cp(Ph2SN)TiCl2 and Cp*(Ph2SN)TiCl2. The second half of this document discusses our attempts to prepare late transition metal phosphinimide complexes; we were particularly interested in preparing analogues of cobaltocene (Cp2Co) and half-sandwich cobalt(I) (CpCo) analogues. A series of new cobalt(II) phosphinimide complexes were prepared by the addition of lithium di(i-propyl)amide (LDA) to cobalt(II) phosphinimine coordination complexes. Continuing studies in this area revealed that cobalt(II) phosphinimide complexes are reactive towards electrophilic and acidic compounds; this led to the isolation of other new cobalt(II) phosphinimide clusters and cobalt(II) phosphinimine complexes.
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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