The complexes Cp(,2)M(SH)(,2), where M = Ti and Zr, have been prepared and treated with S(,8) and >N-S(,x)-NN = benzimidazolyl, phthalimidyl and x = 1, 2, to give the metallacyclohexasulfanes Cp(,2)MS(,5). Reaction of Cp(,2)TI(SH)(,2) with >N-SR, where >N = phthalimidyl, succinimidyl, gave the complexes Cp(,2)Ti(S(,2)R)(,2) (R = CHMe(,2)) and Cp(,2)Ti(SR)(S(,3)R) (R = Ph, 4-C(,6)H(,4)Me). The thiolates Cp(,2)Ti(Cl)SR and Cp(,2)Ti(SR)(,2) (R = CHMe(,2), CMe(,3), Ph, 4-C(,6)H(,4)Me) were prepared for comparison. Treatment of the complexes Cp(,2)MCl(,2) with anhydrous solutions of Li(,2)E(,x) gave the complexes Cp(,2)ME(,5), where M = Ti, Zr, Hf and E = S, Se. The compounds (RCp)(,2)TiS(,5) (R = Me, SiMe(,3)),CH(,2)Cp(,2)TiS(,5), and (Me(,5)Cp)CpTiS(,5) were prepared similarly. Reaction of Li(,2)S(,x) with (Me(,5)Cp)(,2)MCl(,2) gave the metallacyclotetrasulfanes (Me(,5)Cp)(,2)MS(,3). The complex Cp(,2)Ti{S(CH(,2))(,3)S} was synthesized. Variable temperature ('1)H NMR studies established the barriers ((DELTA)G('(NOT=))) for ME(,x) and TiS(,2)C(,3) ring reversal in the above complexes. The crystal structures of Cp(,2)Ti(SPh)(S(,3)Ph), Cp(,2)MS(,5), and (Me(,5)Cp)(,2)TiS(,3) are discussed.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.71837 |
| Date | January 1983 |
| Creators | McCall, James M. |
| 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: 000172259, proquestno: AAINK64552, Theses scanned by UMI/ProQuest. |
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