New compositions containing carbon and sulfur
Using a soluble source of $\alpha$-$\rm C\sb3S\sb5\sp{2-}$, $\rm (NBu\sb4)\sb2\lbrack Zn(\alpha$-$\rm C\sb3S\sb5)\sb2\rbrack$, pure $\rm\lbrack C\sb3S\sb5\rbrack\sb{\rm n}$ was prepared via oxidation with sulfuryl chloride and its relationship to the dimer $\rm C\sb6S\sb{10}$ reinvestigated. Treatment of the zinc reagent with HCl resulted in formation of the dithiol $\rm C\sb3S\sb5H\sb2$. Thermolysis of the dithiol gave the carbon sulfide $\rm C\sb6S\sb8$. Both $\rm C\sb6S\sb{10}$ and $\rm C\sb6S\sb8$ were converted to dioxo derivatives by treatment with Hg$\sp{2+}$. For $\rm C\sb6S\sb{10}$, the O for S exchange reaction is accompanied by a structural change in which a portion of the molecule rearranges to a 1,2,3,6-tetrathiacycloheptadiene ring. Oxidative addition of $\rm C\sb4S\sb6$ to $\rm (C\sb5H\sb5)\sb2Ti(CO)\sb2$ afforded the titanium complex $\rm (C\sb5H\sb5)\sb2TiC\sb4S\sb6$. This complex reacts with thiophosgene to yield the carbon sulfide $\rm C\sb5S\sb7$.
University of Illinois - Urbana-Champaign
Networked Digital Library of Theses and Dissertations
University of Illinois at Urbana-Champaign