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 journalArticlepeer-review

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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