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 Title: New compositions containing carbon and sulfur Author(s): Galloway, Collin Patrick Doctoral Committee Chair(s): Rauchfuss, Thomas B. Department / Program: Chemistry, Inorganic Discipline: Chemistry, Inorganic Degree Granting Institution: University of Illinois at Urbana-Champaign Degree: Ph.D. Genre: Dissertation Subject(s): Chemistry, Inorganic 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. Issue Date: 1994 Type: Text Language: English URI: http://hdl.handle.net/2142/23550 Rights Information: Copyright 1994 Galloway, Collin Patrick Date Available in IDEALS: 2011-05-07 Identifier in Online Catalog: AAI9503191 OCLC Identifier: (UMI)AAI9503191
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