TY - JOUR
T1 - Olefin metathesis for metal incorporation
T2 - Preparation of conjugated ruthenium-containing complexes and polymers
AU - Bolton, Sarah L.
AU - Schuehler, Danielle E.
AU - Niu, Xiang
AU - Gopal, Lakshmi
AU - Sponsler, Michael B.
N1 - Funding Information:
We thank the National Science Foundation (CHE-0320583) the donors of The Petroleum Research Fund, administered by the American Chemical Society, for support of this research.
PY - 2006/12/1
Y1 - 2006/12/1
N2 - 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.
AB - 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.
KW - Alkylidene
KW - Olefin metathesis
KW - Ruthenium
UR - http://www.scopus.com/inward/record.url?scp=33751237372&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=33751237372&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2006.08.085
DO - 10.1016/j.jorganchem.2006.08.085
M3 - Article
AN - SCOPUS:33751237372
VL - 691
SP - 5298
EP - 5306
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
SN - 0022-328X
IS - 24-25
ER -