University of Illinois Urbana-Champaign

Cysteine(2-), alkyl, and siloxide complexes of ruthenium(VI) and iron(III)

Bigham, Wilson Stuart

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Description

Title
Cysteine(2-), alkyl, and siloxide complexes of ruthenium(VI) and iron(III)
Author(s)
Bigham, Wilson Stuart
Issue Date
1992
Doctoral Committee Chair(s)
Shapley, Patricia A.
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
Language
eng
Abstract
Transition metal-cysteine complexes are reviewed in Chapter 1. Compounds for which X-ray crystal structures have been determined are considered first followed by those for which only spectroscopic evidence exists. The synthesis and characterization of several trans-dioxoruthenium(VI) species containing cysteine(2$-)$ and related ligands is reported in Chapter 2. The compounds $\rm Ru(O)\sb2(py)\sb2(SC\sb2H\sb5)\sb2,$ Ru(O)$\sb2$(py)$\sb2\{$SCH$\sb2$CH$\sb2$C(O)O$\},$ Ru(O)$\sb2$(bpy)$\{$SCH$\sb2$CH(NCHO)C(O)O$\},$ Ru(O)$\sb2$(py)$\{$SCH$\sb2$CH(NHCOMe)C(O)O$\},$ and Ru(O)$\sb2$(bpy)$\{$SCH$\sb2$CH(NHCOMe)C(O)O$\}$ have been synthesized in yields ranging from 60-87% from Ru(O)$\sb2$(OH)$\sb2$(py)$\sb2$ and Ru(O)$\sb2$Cl$\sb2$(bpy) using either ethane thiol, 3-mercaptopropionic acid, N-acetyl-L-cysteine, or N-formyl-L-cysteine. The iron(II) and iron(III) complexes (NBu$\sb4\rbrack\sb{\rm n}$ (Fe(SCH$\sb2$CH(NHCOCH$\sb3)$COO)$\sb2$) (n = 1,2) have been synthesized by the addition of two equivalents of N-aceteyl-L-cysteine to methylene chloride solutions of either (NBu$\sb4$) (Fe$\sp{\rm III}$(OSiMe$\sb3)\sb4$) or (NBu$\sb4\rbrack\sb2$(Fe$\sp{\rm II}$(OSiMe$\sb3)\sb4$) and are described in Chapter 3. The synthesis and characterization of the first monooxo ruthenium(VI) tetraalkyl complex, (Ru(O)(CH$\sb2$Si(CH$\sb3)\sb3)\sb4$), is reported in Chapter 4 along with that for Ru(CH$\sb2$Si(CH$\sb3)\sb3)\sb4.$ These complexes are readily synthesized from trans-(PPN) $\sb2$(Ru(O)$\sb2$Cl$\sb4$) and either four or ten equivalents of trimethylsilyl-methylmagnesium chloride in THF or methylene chloride respectively. In Chapter 5, combination of (C$\sb5$H$\sb9)\sb7$Si$\sb7$O$\sb{12}$H$\sb3$ with either (NBu$\sb4$) (Fe(OSiMe$\sb3)\sb4$) or (NBu$\sb4$) (Fe(Cl)$\sb4$) and triethylamine gives the iron-containing silsesquioxanes (NBu$\sb4$) ((C$\sb5$H$\sb9)\sb7$Si$\sb7$O$\sb{12}$FeCl) and (NBu$\sb4$) ((C$\sb5$H$\sb9)\sb7$Si$\sb7$O$\sb{12}$FeOSi(CH$\sb3)\sb3$) in yields of at least 60% after recrystallization from toluene/hexane. These complexes can be modified by substitution for the free siloxide or chloride ligand to give (NBu$\sb4$) ($\{$(C$\sb5$H$\sb9)\sb7$Si$\sb7$O$\sb{12}$Fe$\}\sb2$O), (NBu$\sb4$) ((C$\sb5$H$\sb9)\sb7$Si$\sb7$O$\sb{12}$FeOOC(CH$\sb3)\sb3$), and (NBu$\sb4$) ((C$\sb5$H$\sb9)\sb7$Si$\sb7$O$\sb{12}$Fe(S-cysteine-OMe)).
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text
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Copyright and License Information
Copyright 1992 Bigham, Wilson Stuart

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