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 language | English (US) |
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Pages (from-to) | 5298-5306 |
Number of pages | 9 |
Journal | Journal of Organometallic Chemistry |
Volume | 691 |
Issue number | 24-25 |
DOIs | |
State | Published - Dec 1 2006 |
Keywords
- Alkylidene
- Olefin metathesis
- Ruthenium
ASJC Scopus subject areas
- Biochemistry
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry
- Materials Chemistry