Synthesis of New Ruthenium Complexes for Propargylic Substitution Reactions
Koo, Dong Hyun 1977-
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This thesis is concerned with the synthesis of monomeric ruthenium complexes and diruthenium complexes with Tp or Cp derivatives and their ruthenium-catalyzed propargylic substitution reactions. First, the mononuclear ruthenium complex, ClTpRu(COD)Cl was synthesized by the simple method of treating TpRu(COD)Cl with sulfonyl chloride. The catalytic activity for propargylic substitution reactions with aromatic propargylic alcohols was good, but the substrate scope was limited to those substrates. Second, reactions of [Cp^RuCl(µ-Cl)2RuCp^Cl] (Cp^ : 1,4-di-tert-butyl-2-neopentyl-3-methoxy-cyclopenta-1,3-diene) with MeSSiMe3 in CH2Cl2 at room temperature afforded two types of thiolate-bridged dinuclear Ru(III) complexes [Cp^Ru(u-SMe)3RuCp^]Cl or [Cp^RuCl(µ-SMe)2RuCp^Cl] depending upon the number of equivalents of MeSSiMe3. Reaction of Cp^RuCl(µ-Cl)RuCp^Cl] with excess MeSSiMe3 in CH2Cl2 resulted in the formation of the triply bridged complex, [Cp^Ru(µ-SMe)3RuCp^]Cl, and 3 equivalent MeSSiMe3 afforded the doubly bridged diruthenium complex, [Cp^RuCl(µ-SMe)2RuCp^Cl]. X-ray crystallography was used to determine their detailed structures, and their catalytic properties were explored in the propargylation of nucleophiles.