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Title:Studies on binary carbon sulfides and their metal complexes
Author(s):Yang, Xiaoguang
Doctoral Committee Chair(s):Rauchfuss, Thomas B.
Department / Program:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Subject(s):Chemistry, Inorganic
Chemistry, Organic
Chemistry, Polymer
Abstract:Seven stable molecular carbon sulfides were known before we started our work. The reaction of Cp$\sb2$TiC$\sb3$S$\sb5$ with one equivalent of S$\sb2$Cl$\sb2$ gave two carbon polysulfides C$\sb3$S$\sb8$ (1) and C$\sb6$S$\sb{12}$ (2). The eclipsed conformation of C$\sb6$S$\sb{12}$ (2) is noteworthy.
The first inorganic tetathiocin C$\sb6$S$\sb{10}$ (3) has been synthesized from the oxidation of (Zn(C$\sb3$S$\sb5$)$\sb2$) $\sp{2-}$ with SO$\sb2$Cl$\sb2$. C$\sb6$S$\sb{10}$ molecules stack in the crystal to form 2-dimensional layered structure with CS$\sb2$ solvate in the channels formed by these layers. (3) was found to react with dimethylacetylenedicarboxylate (DMAD) to give C$\sb3$S$\sb5$ $\cdot$ DMAD.
The reaction of (Zn($\beta$-C$\sb3$S$\sb5$)$\sb2$) $\sp{2-}$ with SOCl$\sb2$ gave $\beta$-C$\sb6$S$\sb8$ (4) and $\beta$-C$\sb6$S$\sb{10}$ (5) along with the C-S polymers. $\beta$-C$\sb6$S$\sb8$ (4), the first known planar 1,4-dithiin, features fused 1,2-dithiole-3-thione rings conjugated with a central 1,4-dithiin ring to form a 22 $\pi$ electron aromatic system.
Studies on the coordination chemistry of C$\sb2$S$\sb4$ $\cdot$ DMAD$\sp{2-}$ uncovered the first planar C$\sb2$S$\sb4$ bridging dinickel dithiolene complex (6). Its crystal structure revealed that $\{$C$\sb2$S$\sb4$ (Ni(C$\sb2$S$\sb4$ $\cdot$ DMAD)$\sb2$) $\sb2\}\sp{2-}$ is virtually planar with the central core C$\sb2$S$\sb4$(NiC$\sb2$S$\sb4$)$\sb2$ about 15A long.
Attempts to synthesize (C$\sb2$S$\sb{\rm x}$)$\sb{\rm n}$ polymer from tetrathiapetalenedione (TPD) led to the synthesis of (dppe)Ni(C$\sb4$S$\sb{11}$) (7) and possible C$\sb4$S$\sb{14}$. The structures of C$\sb4$S$\sb{11}\sp{2-}$ chelate is thought to resemble a subunit in (C$\sb2$S$\sb4$)$\sb{\rm x}$. Attempts to prepare (C$\sb2$S$\sb{\rm x}$)$\sb{\rm n}$ from ((MeCp)$\sb2$Ti) $\sb2$($\mu$-C$\sb2$S$\sb4$) afforded hydrocarbon-contaminated samples of the desired polymer.
Tetrathiapentalenedione (TPD), C$\sb2$S$\sb4$(CO)$\sb2$, reacts with MS$\sb4\sp{2-}$ (M = Mo, W) to give M(S$\sb2$C$\sb2$S$\sb2$CO)$\sb3\sp{2-}$. Similarly, C$\sb2$S$\sb4$(CO)(CS) and WS$\sb4\sp{2-}$ give W(S$\sb2$C$\sb2$S$\sb2$CS)$\sb3\sp{2-}$ and together with (W$\sb2$S$\sb4$(S$\sb2$C$\sb2$S$\sb2$CS)$\sb2$) $\sp{2-}$. The same compounds can be obtained by the action of WS$\sb4\sp{2-}$ with the cyclic bis(disulfide) (S$\sb2$C$\sb2$S$\sb2$CS)$\sb2$. Electrochemical studies show that (M(S$\sb2$C$\sb2$S$\sb2$CE)$\sb3$) $\sp{2-}$ (M = Mo, W; E = S, O) undergo two one-electron oxidations at mild potentials, giving the charge neutral inorganic complexes MC$\sb6$S$\sb{15}$ and MC$\sb6$O$\sb3$S$\sb{12}$.
Issue Date:1990
Rights Information:Copyright 1990 Yang, Xiaoguang
Date Available in IDEALS:2011-05-07
Identifier in Online Catalog:AAI9114473
OCLC Identifier:(UMI)AAI9114473

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