Synthesis and Reactivity of Some Organometallic Chalcogenide Complexes

Examples of Sila-1,1-dithiolate complexes, Cp$\sb2$MS$\sb2$SiMe$\sb2$ (M = Ti (8) and V) and PtS$\sb2$SiMe$\sb2$(P(C$\sb6$H$\sb5$)$\sb3$)$\sb2$, were prepared by treating (Me$\sb2$SiS)$\sb3$/Li$\sb2$S with the metal dichlorides. Compound 8 is particularly interesting because it contains two potentially reactive sites; Ti-S and Si-S bonds. The reaction of 8 with transition metal (or main group) dichlorides affords Cp$\sb2$TiCl$\sb2$ ($>$90%) without the formation of Me$\sb2$SiCl$\sb2$. Indicating that reaction at titanium is preferred. The reactivity of Cp$\sb2$TiS$\sb2$SiMe$\sb2$ with oxometallates gave sulfiding reactions, without reduction occurring. Compound 8 converts WO$\sb{\rm x}$S$\sb{\rm 4-x}\sp{2-}$ (X = 4, 3, 2) and TaW$\sb5$O$\sb \sp{3-}$ into WS$\sb4\sp{2-}$ and TaW$\sb5$O$\sb $S$\sp{3-}$, respectively.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2014

Author dc:creator

• Giolando, Dean Mark

• Chemistry, Inorganic

Identifier

(UMI)AAI8721640

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70370