The complexes CpRu(PPh$ sb3)$(L)SR (Cp=$ eta sp5$-cyclopentadienyl; R=CMe$ sb3,$ CHMe$ sb2,$ 4-$ rm C sb6H sb4Me)$ reacted with NOBF$ sb4$ to give either (CpRu(PPh$ sb3)$(NO)SR) BF$ sb4$ (L=PPh$ sb3)$ or complexes containing disulfide ligands (L=CO). The bisphosphine complexes, CpRu(PPh$ sb3) sb2$SR, reacted with HBF$ sb4$ to give the corresponding thiol complex salts (CpRu(PPh$ sb3) sb2$(HSR)) BF$ sb4$ and with (MeSSME$ rm sb2 rbrack BF sb4$ to give (CpRu(PPh$ sb3) sb2$(SMe$ sb2)$) BF$ sb4$ regardless of the starting thiolates. The complexes CpRu(PPh$ sb3) sb2$SR reacted with the sulfur transfer agent MeSphth (phth=phthalimido) to give CpRu (PPh$ sb3) sb2$(phth) and the dimers ($ mu$-SMe)($ mu$-SR) (CpRu(phth)) $ sb2$ for R=CMe$ sb3$ or CHMe$ sb2,$ while for R=4-$ rm C sb6H sb4Me$ the same reaction gave CpRu(PPh$ sb3)$(phth)(MeSS-4-$ rm C sb6H sb4Me)$ and ($ mu$-SMe)($ mu$-S-4-$ rm C sb6H sb4$Me) (CpRu(S-4-$ rm C sb6H sb4Me) rbrack sb2.$ The complex CpRu(PPh$ sb3) sb2$ SCH$ sb2$CH=CH$ sb2,$ prepared from the reaction of CpRu(PPh$ sb3) sb2$Cl and LiSCH$ sb2$CH=CH$ sb2,$ reacted with CO and CS$ sb2$ to give CpRu(PPh$ sb3)$(CO)SCH$ sb2$CH=CH$ sb2$ and CpRu(PPh$ sb3)$S$ sb2$CSCH$ sb2$CH=CH$ sb2,$ respectively. Refluxing a toluene solution of CpRu(PPh$ sb3) sb2$SCH$ sb2$CH=CH$ sb2$ gave ($ mu sb3$-S)$ sb2( mu$-SCH$ sb2$CH=CH$ sb2$) (CpRu) $ sb3$ in which the C-S bond has been cleaved. / The complexes (PPh$ sb3) sb2$Pt(SR)$ sb2$ (R=H, $ rm CMe sb3, CHMe sb2,$ 4-$ rm C sb6H sb4Me)$ were treated with SO$ sb2$ as models for the Claus process. These reactions produced adducts of formula (PPh$ sb3) sb2$Pt(S(SO$ sb2)$R)$ sb2,$ which have a labile thiolate-bound SO$ sb2$ molecule, for R=CMe$ sb3,$ 4-$ rm C sb6H sb4Me$ and CHMe$ sb2.$ The reaction of cis-(PPh$ sb3) sb2$Pt(SH)$ sb2$ with SO$ sb2$ gave (PPh$ sb3) sb2$Pt(S$ sb3$O) and H$ sb2$O, a reaction which mimics Claus chemistry. The complexes cis-(PPh$ sb3) sb2$Pt(SH)$ sb2,$ (PPh$ sb3) sb2$Pt(S$ sb3$O) and (PPh$ sb3) sb2$Pt(SR)$ sb2$ catalyze the Claus reaction (2H$ sb2$S + SO$ rm sb2 to3/8S sb8+2H sb2O).$ / The complexes (PPh$ sb3) sb2$Pt(SR)$ sb2$ reacted with CS$ sb2$ to form the mixed thiolato-thioxanthato complexes (PPh$ sb3)$Pt(SR)(S$ sb2$CSR) wherein CS$ sb2$ had inserted into one of the Pt-S bonds. The complex cis-(PPh$ sb3) sb2$Pt(SH)$ sb2$ reacted with CS$ sb2$ to give the known complex, (PPh$ sb3) sb2$Pt(S$ sb2$CS), which contains a trithiocarbonate group. / The structures of (CpRu(PPh$ sb3)$(NO)SCMe$ rm sb3 rbrack BF sb4, ( mu$-SMe)($ mu$-S-4-$ rm C sb6H sb4Me)$ (CpRu(S-4-$ rm C sb6H sb4Me) rbrack sb2, ( mu sb3$-S)$ sb2( mu$-SCH$ sb2$CH=CH$ sb2)$ (CpRu) $ sb3,$ (PPh$ sb3) sb2$Pt(S$ sb3$O) and (PPh$ sb3)$Pt(S-4-$ rm C sb6H sb4Me)$(S$ sb2$CS-4-$ rm C sb6H sb4Me)$ were determined by x-ray crystallography.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.40111 |
| Date | January 1996 |
| Creators | El-khateeb, Mohammad |
| Contributors | Shaver, Alan (advisor) |
| 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: 001500052, proquestno: NN12361, Theses scanned by UMI/ProQuest. |
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