Olefin metathesis for metal incorporation: Preparation of conjugated ruthenium-containing complexes and polymers

Sarah L. Bolton, Danielle E. Schuehler, Xiang Niu, Lakshmi Gopal, Michael B. Sponsler

Research output: Contribution to journalArticle

11 Scopus citations

Abstract

Olefin Metathesis for Metal Incorporation (OMMI) was used for the stoichiometric attachment of ruthenium to both small and large polyenes. The dinuclear complexes (PCy3)2C12Ru{double bond, long}CH(CH{double bond, long}CH)nCH{double bond, long}Ru(PCy3)2Cl2 (n = 1, 2), were prepared by reacting 2 equiv. of the Grubbs first-generation catalyst (PCy3)2C12Ru{double bond, long}(CHPh)) with 1 equiv. of the appropriate polyene (1,3,5-hexatriene for n = 1 and 1,3,5,7-octatetraene for n = 2). Use of excess hexatriene led to the formation of the monoruthenium complex (PCy3)2C12Ru{double bond, long}CHCH{double bond, long} CHCH{double bond, long}CH2. The mono- and di-ruthenium complexes exhibited marked differences in their spectroscopic and electrochemical properties, in addition to their Z-E isomerization rates. Nucleophilic attack of PCy3 on the end CH2 of the mono complex was observed, leading to both isomerization and phosphonium products. Extending the OMMI strategy to the second-generation catalyst was also done, despite the reduced initiation rate. The more reactive catalyst (H2IMes)RuCl2({double bond, long}CHPh)(3-bromopyridine)2 allowed for ruthenium incorporation into polyacetylene, leading to the formation of polymers and oligomers with high ruthenium content.

Original languageEnglish (US)
Pages (from-to)5298-5306
Number of pages9
JournalJournal of Organometallic Chemistry
Volume691
Issue number24-25
DOIs
StatePublished - Dec 1 2006

Keywords

  • Alkylidene
  • Olefin metathesis
  • Ruthenium

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

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