Organometallic and Inorganic Derivatives of the Tetrathiometallates

In an effort to study the tetrathiometallates as ligands in heterometallic complexes, which may bind π-acidic coligands, the preparation of a number of low-valent organometallic derivatives of MoS$\sb4\sp{2-}$ and WS$\sb4\sp{2-}$ was undertaken. The complex ((COD)Rh) $\sb2$WS$\sb4$ 1 was prepared from the direct reaction of equimolar amounts of ((COD)RhCl) $\sb2$ and (Ph$\sb4$P)$\sb2$WS$\sb4$. Compound 1 was found to exhibit extensive ligand substitution chemistry, involving organophosphines, CO, and $t$-BuNC. It was found that 1 could only support two strongly π-acidic CO ligands; ((PPh$\sb3$)(CO)Rh) $\sb2$WS$\sb4$ was found to be the stable species. The reaction of Pd(WS$\sb4)\sb2\sp{2-}$ with an equimolar amount of ((COD)RhCl) $\sb2$ gave the insoluble species, (COD)Rh(μ-S)$\sb2$W(μ-S)$\sb2$Pd(μ-S)$\sb2$W(μ-S)$\sb2$Rh(COD). This complex reacted with excess PPh$\sb3$, giving the CH$\sb2$Cl$\sb2$-soluble species: (PPh$\sb3)\sb2$Rh(μ-S)$\sb2$W(μ-S)$\sb2$Pd(μ-S)$\sb2$W(μ-S)$\sb2$Rh(PPh$\sb3)\sb2$.

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

• Howard, Kevin Edward

Contributors dc:contributor

• Rauchfuss, Thomas B.

• Chemistry, Inorganic

Identifier

(UMI)AAI8908710

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70424