Impact of electronic modification of the chelating benzylidene ligand in cis-dichloro-configured second-generation olefin metathesis catalysts on their activity
Type
ArticleAuthors
Pump, Eva
Poater, Albert

Zirngast, Michaela
Torvisco, Ana
Fischer, Roland C.
Cavallo, Luigi

Slugovc, Christian
KAUST Department
Chemical Science ProgramKAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Date
2014-05-27Online Publication Date
2014-05-27Print Publication Date
2014-06-09Permanent link to this record
http://hdl.handle.net/10754/563594
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Show full item recordAbstract
A series of electronically modified second-generation cis-dichloro ruthenium ester chelating benzylidene complexes was prepared, characterized, and benchmarked in a typical ring-opening metathesis polymerization (ROMP) experiment. The electronic tuning of the parent chelating benzylidene ligand (2-ethyl ester benzylidene) was achieved by substitution at the 4- and 5-positions with electron-withdrawing nitro or electron-donating methoxy groups. The effect of the electronic tuning on the cis-trans isomerization process was studied experimentally and theoretically. Density functional theory calculations clearly revealed the influence of electronic modification on the relative stability between the cis and trans isomers, which is decisive for the activity of the studied compounds as initiators in ROMP. © 2014 American Chemical Society.Citation
Pump, E., Poater, A., Zirngast, M., Torvisco, A., Fischer, R., Cavallo, L., & Slugovc, C. (2014). Impact of Electronic Modification of the Chelating Benzylidene Ligand in cis-Dichloro-Configured Second-Generation Olefin Metathesis Catalysts on Their Activity. Organometallics, 33(11), 2806–2813. doi:10.1021/om500315tSponsors
E.P. gratefully acknowledges the receipt of the "Chemical Monthly Fellowship" financed by Springer Verlag, the Austrian Academy of Sciences (OAW), and the Gesellschaft Osterreichischer Chemiker (GOCH). A.P. thanks the Spanish MICINN for a Ramon y Cajal contract (RYC-2009-05226) and the European Commission for a Career Integration Grant (CIG09-GA-2011-293900).Publisher
American Chemical Society (ACS)Journal
OrganometallicsRelations
Is Supplemented By:- [Dataset]
Pump, E., Poater, A., Zirngast, M., Torvisco, A., Fischer, R., Cavallo, L., & Slugovc, C. (2014). CCDC 977279: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc11sy4x. DOI: 10.5517/cc11sy4x HANDLE: 10754/624297 - [Dataset]
Pump, E., Poater, A., Zirngast, M., Torvisco, A., Fischer, R., Cavallo, L., & Slugovc, C. (2014). CCDC 977280: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc11sy5y. DOI: 10.5517/cc11sy5y HANDLE: 10754/624298 - [Dataset]
Pump, E., Poater, A., Zirngast, M., Torvisco, A., Fischer, R., Cavallo, L., & Slugovc, C. (2014). CCDC 977278: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc11sy3w. DOI: 10.5517/cc11sy3w HANDLE: 10754/624296
ae974a485f413a2113503eed53cd6c53
10.1021/om500315t