A Flexible and Modular Approach to [2]Ferrocenophanes with Nitrogen in Bridging Position
| dc.contributor.advisor | Mueller, Jens | |
| dc.contributor.committeeMember | Ward, Dale | |
| dc.contributor.committeeMember | Foley, Stephen | |
| dc.contributor.committeeMember | Bowles, Richard | |
| dc.creator | Dey, Subhayan 1987- | |
| dc.creator.orcid | 0000-0002-5910-0423 | |
| dc.date.accessioned | 2016-10-07T17:53:46Z | |
| dc.date.available | 2017-11-27T16:32:00Z | |
| dc.date.created | 2016-09 | |
| dc.date.issued | 2016-10-07 | |
| dc.date.submitted | September 2016 | |
| dc.date.updated | 2016-10-07T17:53:46Z | |
| dc.description.abstract | [n]Ferrocenophanes are interesting because these strained sandwich compounds can be polymerized to metallopolymers by ring-opening polymerization reactions. Although there are many strained [n]ferrocenophanes known, only few of them can be polymerized with controlled molecular weight and molecular weight distribution. Among them, the Me2¬Si-bridged [1]ferrocenophane is the mostly explored species. To expand the possibility of accessible monomers we synthesized a new class of strained [2]ferrocenophanes. Although there are plenty of examples of symmetrically bridged [2]ferrocenophanes known, similar species with two different bridging elements are comparatively rare. In order to induce a difference in polarity over the diatomic bridge, nitrogen was introduced in the bridging position. Via a known synthetic methodology, one bromine of 1,1'-dibromoferrocene was selectively replaced by an amino group. The resulting compound was then modified into a class of easily synthesizable starting materials which were cleanly lithiated under optimized condition and in-situ reacted with different elemental dihalides to produce unsymmetrically bridged aza[2]ferrocenophanes. This is the first reported development of a modular synthetic approach towards this class of strained sandwich compounds. Aza[2]ferrocenophanes with boron, gallium, silicon, tin, and phosphorus as the second bridging element were prepared and characterized. Among these strained compounds, only the silicon- and tin-bridged species have been investigated for ring-opening polymerizations. However, no polymeric materials were obtained from these reactions. The preparation of azaphospha[2]ferrocenophanes was surprisingly difficult and led to unexpected products like 1,1'-disubstituted ferrocenes and azacarbaphospha[3]ferrocenophane. | |
| dc.format.mimetype | application/pdf | |
| dc.identifier.uri | http://hdl.handle.net/10388/7522 | |
| dc.subject | Metallocenophane, Ferrocenophane, Silicon, Tin, Phosphorus, Boron, Ring-Opening Polymerization, Metallopolymers. | |
| dc.title | A Flexible and Modular Approach to [2]Ferrocenophanes with Nitrogen in Bridging Position | |
| dc.type | Thesis | |
| dc.type.material | text | |
| local.embargo.terms | 2017-10-07 | |
| thesis.degree.department | Chemistry | |
| thesis.degree.discipline | Chemistry | |
| thesis.degree.grantor | University of Saskatchewan | |
| thesis.degree.level | Doctoral | |
| thesis.degree.name | Doctor of Philosophy (Ph.D.) |