Primary silanes of the type RSiH$ sb3$, where R = phenyl (Ph), benzyl (Bz) and n -hexyl, undergo catalytic dehydrogenative polymerisation in the presence of catalytic amounts of Cp$ sb2$TiMe$ sb2$ (Cp = $ eta sp5$-C$ sb5$H$ sb5)$ to give linear oligomers consisting of about 10 silicon atoms, regardless of the reaction conditions. When the amount of Cp$ sb2$TiMe$ sb2$ was increased, novel organometallic complexes of the type $ {$(Cp$ sb2$Ti)$ sb2( mu$-H)$( mu$-HSiRH)$ }$ and $ {$Cp$ sb2$Ti$( mu$-HSiRH)$ } sb2$ were isolated and characterised. X-ray crystal structural characterisation has confirmed the first Ti-H-Si-Ti bridged systems. Other titanocenes (Cp$ sbsp{2}{ prime}$TiMe$ sb2$(Cp$ sp prime$ = $ eta sp5$-C$ sb5$H$ sb4$Me), (Cp$ sb2$TiH) $ sb{ rm n}$, (Cp$ sb2$Ti) $ sb2$ and Cp$ sb2$Ti(CO)$ sb2)$ also polymerised PhSiH$ sb3,$ and in addition gave analogous complexes under the appropriate conditions. Furthermore PhSiH$ sb3$ undergoes polymerisation in the presence of CpCp$ sp *$TiMe$ sb2$ (Cp$ sp *$ = $ eta sp5$-C$ sb5$Me$ sb5),$ but not Cp$ sbsp{2}{ *}$TiMe$ sb2.$ Polymerisation of RSiH$ sb3$ (R = phenyl and benzyl) also occurs in the presence of Cp$ sb2$ZrMe$ sb2$ and complexes of the type $ {$Cp$ sb2$(SiHMeR)Zr$( mu$-H)$ sb2$Zr(SiH$ sb2$R)Cp$ sb2 }$ have been identified, and isolated (R = phenyl). (Cp$ sb2$ZrH$ sb2$) $ sb{ rm n}$ also polymerises PhSiH$ sb3,$ with the associated production of $ {$Cp$ sb2$Zr$( mu$-H)(SiH$ sb2$Ph)$ } sb2.$ The analogous complex was also observed during the reaction of Cp$ sb2$ZrMe$ sb2$ with BzSiH$ sb3.$ The reactions have been followed by $ sp1$H and $ sp{29}$Si NMR, and possible reaction paths are discussed.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.72099 |
| Date | January 1986 |
| Creators | Aitken, Clare T. (Clare Theresa) |
| Publisher | McGill University |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Format | application/pdf |
| Coverage | Doctor of Philosophy (Department of Chemistry.) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 000417461, proquestno: AAINL44365, Theses scanned by UMI/ProQuest. |
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