Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 57, Issue 44, Pages 14566-14569Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201808233
Keywords
metallacyclobutanes; molybdenum; N-heterocyclic carbenes; olefin metathesis; surface chemistry
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Funding
- SNF (Swiss National Science Foundation) [200021_169134]
- Deutsche Forschungsgemeinschaft (DFG) [BU 2174/19-1, CRC 1333]
- Scholarship Fund of the Swiss Chemical Industry
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Silica-supported cationic Mo-imido alkylidene N-heterocyclic carbene catalysts, prepared by surface organometallic chemistry, display contrasting olefin metathesis activity for terminal and internal olefins. The high metathesis activity towards terminal alkenes is attributed to the strong sigma-donating property of the NHC ancillary ligand, which disfavors the formation of the parent square-planar metallacyclobutane, an off-cycle reaction intermediate resulting from the reaction with ethylene, one of the metathesis products. This tailored ligand environment also allowed the first trigonal bipyramidal (TBP) metallacyclobutane reaction intermediate for supported Mo metathesis catalysts to be identified.
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