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https://hdl.handle.net/2142/23550
Description
Title
New compositions containing carbon and sulfur
Author(s)
Galloway, Collin Patrick
Issue Date
1994
Doctoral Committee Chair(s)
Rauchfuss, Thomas B.
Department of Study
Chemistry, Inorganic
Discipline
Chemistry, Inorganic
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Inorganic
Language
eng
Abstract
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 $\rm C\sb5S\sb7$.
The compound $\rm C\sb3S\sb7O$, a pentathiepin, were isolated from the O for S exchange reaction of $\rm C\sb3S\sb8$ with Hg$\sp{2+}$. This oxo derivative reacted with two equiv. of base to give the planar dianion $\rm C\sb4S\sb6\sp{2-}$. Crystallographic analysis and EHMO calculations showed that it has a delocalized $\pi$ electron system. Crude nickel complexes of this material are semiconducting with conductivities comparable to other thiocarbon metal complexes.
The ferrocene polysulfides $\rm Fe(C\sb5H\sb3)\sb2(S\sb3)\sb2$ and Fe(t-BuC$\rm \sb5H\sb2)(C\sb5H\sb3)(S\sb3)\sb2$ were synthesized from ferrocene and t-butylferrocene using a stepwise lithiation-sulfurization methodology. Upon addition of tributylphosphine, these hexasulfides were desulfurized to yield network polymers. In the case of Fe(t-BuC$\rm \sb5H\sb2)(C\sb5H\sb3)(S\sb3)\sb2$, desulfurization gave a soluble polymer which had high molecular weights as shown by gel permeation chromatography.
The tristitanocene complex, $\rm\lbrack(C\sb5H\sb5)\sb2$Ti) $\rm\sb3C\sb6S\sb6$, was prepared in high yield from benzene hexathiolate, $\rm C\sb6(SNa)\sb6$. Upon treatment of this complex with three equiv. of SCl$\sb2$, the sparingly soluble carbon sulfide $\rm C\sb6S\sb9$ was obtained.
The dimetallic complex $\rm Fe\sb2S\sb2(CO)\sb6$ was reacted photochemically with C$\sb{60}$. Spectroscopic analysis of the products verified the presence of $\rm Fe\sb2S\sb2(CO)\sb6$ adducts of C$\sb{60}$ with the formula $\rm C\sb{60}\lbrack Fe\sb2S\sb2(CO)\sb6\rbrack\sb{n}$, where n = 1-5.
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