University of Illinois Urbana-Champaign

The synthesis and stereodynamics of cyclopentadienyl ruthenium chalcogenide clusters

Houser, Eric Jon

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Description

Title
The synthesis and stereodynamics of cyclopentadienyl ruthenium chalcogenide clusters
Author(s)
Houser, Eric Jon
Issue Date
1994
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
Language
eng
Abstract
  • A diamagnetic salt of the (MeC$\sb5$H$\sb4)\sb4$Ru$\sb4$S$\sb4\sp{2+}$ cluster cation was obtained by oxidation of (MeC$\sb5$H$\sb4)\sb4$Ru$\sb4$S$\sb4$ with ((MeC$\sb5$H$\sb4)\sb2$Fe) PF$\sb6$. Variable temperature $\sp1$H NMR measurements showed that (MeC$\sb5$H$\sb4)\sb4$Ru$\sb4$S$\sb4\sp{2+}$ is dynamic in solution; it exhibits signals for two chiral Ru sites at low temperatures but only one symmetrical Ru environment at high temperatures. Similar dynamic behavior was observed for (MeC$\sb5$H$\sb4)\sb4$Ru$\sb4$Se$\sb4$(PF$\sb6)\sb2$, while samples of (MeC$\sb5$H$\sb4)\sb4$Ru$\sb4$Te$\sb4$(PF$\sb6)\sb2$ showed only slight line broadening at low temperatures. The concentration independence of the coalescence temperature (T$\sb{\rm c}$) of the CH$\sb3$C$\sb5$H$\sb4$ signals showed that the exchange processes are intramolecular. The exchange barrier of (Me$\sb3$SiC$\sb5$H$\sb4)\sb4$Ru$\sb4$S$\sb4$(PF$\sb6)\sb2$ was found to be similar to those of (MeC$\sb5$H$\sb4)\sb4$Ru$\sb4$E$\sb4$(PF$\sb6)\sb2$ (E = S, Se), which indicates that the exchange processes do not involve hindered RCp rotation. The activation parameters were evaluated from analyses of the line shapes as a function of temperature; the free energies of activation range from 52 to 55 kJ/mol for all clusters.
  • ((MeC$\sb5$H$\sb4)\sb4$Ru$\sb4$S$\sb3$(SCH$\sb3)$) CF$\sb3$SO$\sb3$ was obtained by the reaction of (MeC$\sb5$H$\sb4)\sb4$Ru$\sb4$S$\sb4$ with CH$\sb3$SO$\sb3$CF$\sb3$. Oxidation of ((MeC$\sb5$H$\sb4)\sb4$Ru$\sb4$S$\sb3$(SCH$\sb3$)) CF$\sb3$SO$\sb3$ with (Cp$\sb2$Fe) PF$\sb6$ yielded ((MeC$\sb5$H$\sb4)\sb4$Ru$\sb4$S$\sb3$(SCH$\sb3$)) (PF$\sb6)\sb2$CF$\sb3$SO$\sb3$. Both clusters exhibited dynamic behavior.
  • Salts of (C$\sb5$Me$\sb5)\sb3$Ru$\sb3$S$\sb4\sp+$ were obtained by reaction of (C$\sb5$Me$\sb5$)Ru(CH$\sb3$CN)$\sb3\sp+$ with (C$\sb5$Me$\sb5)\sb2$Ru$\sb2$S$\sb4$. The solid state structure of (C$\sb5$Me$\sb5)\sb3$Ru$\sb3$S$\sb4$(PF$\sb6$) showed that the cluster cation contains a new bonding mode for a persulfide ligand and defines a new structural motif for M$\sb3$S$\sb4$ clusters. Electrophiles react with (C$\sb5$Me$\sb5)\sb3$Ru$\sb3$S$\sb4\sp+$ and add to the bridging sulfur atoms. The core structure of the SO$\sb2$ adduct (C$\sb5$Me$\sb5)\sb3$Ru$\sb3$S$\sb3$(S$\sb2$O$\sb2)\sp+$ differs from that of (C$\sb5$Me$\sb5)\sb3$Ru$\sb3$S$\sb4\sp+$ in that it only has one persulfide ligand.
  • The reaction of tetramethyltetrathiafulvalene (TMTTF) with Fe$\sb4$S$\sb4$(NO)$\sb4$ gave the one-dimensional charge transfer salt (TMTTF)$\sb2$Fe$\sb4$S$\sb4$(NO)$\sb4$. Solid state measurements showed this material to be a paramagnetic semiconductor.
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Copyright and License Information
Copyright 1994 Houser, Eric Jon

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