Cp$ sb2$Ti(C))$ sb2$, where Cp = $ eta sp5$-cyclopentadienyl, reacted with RSSSR to give the catenated sulfur complexes Cp$ sb2$Ti(SR)(SSR), where R = CMe$ sb3$, CHMe$ sb2$, CH$ sb2$Ph, p-C$ sb6$H$ sb4$Me and CPh$ sb3$. These complexes, except for R = CPh$ sb3$, reacted with PhCH$ sb2$Br to give Cp$ sb2$TiBr$ sb2$, PhCH$ sb2$SR and PhCH$ sb2$SSR as major products. Cp$ sb2$Ti(SR)(SSR) desulfurized slowly in solution and rapidly in the presence of Ph$ sb3$P, giving Cp$ sb2$Ti(SR)$ sb2$ and Ph$ sb3$PS, in addition to other species. Similarly, phth-SSR, where phth = phthalimide, oxidatively added to Cp$ sb2$Ti(CO)$ sb2$ to give Cp$ sb2$Ti(X)(SSR), where X = phth and R = CMe$ sb3$, CHMe$ sb2$, CH$ sb2$Ph and p-C$ sb6$H$ sb4$Me. Solvolysis by MeOH and EtOH gave the species where X = OMe and OEt. In a similar manner Ph$ sb3$CSSCl added to Cp$ sb2$Ti(CO)$ sb2$ to give Cp$ sb2$Ti(Cl)(SSCPh$ sb3$). Treatment of Cp$ sb2$Ti(SR)(SSR) with (norbornadiene)Mo(CO)$ sb4$ gave the bridged dimers, (Cp$ sb2$Ti($ mu$-SR)-($ mu$-S$ sb{ rm x}$R)Mo(CO)$ sb4$), where x = 1 and 2 and R = CMe$ sb3$ and CHMe$ sb2$. The complexes where x = 2 contained the rare iso-$ mu$-$ eta sp1$-SSR ligand. In solution at low temperatures the bridging thiolato and disulfano groups were predominantly transoid. At higher temperatures, a dynamic process that allowed averaging of cyclopentadienyl ring environments took place. $ sp1$H NMR studies permitted evaluation of $ Delta{ rm G sbsp{c}{ ddagger}}$ for the averaging process.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.75828 |
| Date | January 1987 |
| Creators | Morris, Stephen Arthur |
| 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: 000665162, proquestno: AAINL46219, Theses scanned by UMI/ProQuest. |
Page generated in 0.0014 seconds