Studies on binary carbon sulfides and their metal complexes

Yang, Xiaoguang

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Description

Title

Studies on binary carbon sulfides and their metal complexes

Author(s)

Yang, Xiaoguang

Issue Date

1990

Doctoral Committee Chair(s)

Rauchfuss, Thomas B.

Department of Study

Chemistry

Discipline

Chemistry

Degree Granting Institution

University of Illinois at Urbana-Champaign

Degree Name

Ph.D.

Degree Level

Dissertation

Keyword(s)

• Chemistry, Inorganic
• Chemistry, Organic
• Chemistry, Polymer

Language

eng

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$\sb{12}$.

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Copyright 1990 Yang, Xiaoguang

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