Promoting Terminal Olefin Metathesis with a Supported Cationic Molybdenum Imido Alkylidene N‐Heterocyclic Carbene Catalyst

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 σ‐donating...

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Published inAngewandte Chemie International Edition Vol. 57; no. 44; pp. 14566 - 14569
Main Authors Pucino, Margherita, Inoue, Mariko, Gordon, Christopher P., Schowner, Roman, Stöhr, Laura, Sen, Suman, Hegedüs, Csaba, Robé, Emmanuel, Tóth, Flórián, Buchmeiser, Michael R., Copéret, Christophe
Format Journal Article
LanguageEnglish
Published Germany Wiley Subscription Services, Inc 26.10.2018
EditionInternational ed. in English
Subjects
Alkenes
Alkylidene
Catalysis
Catalysts
Cations
Decomposition reactions
Ligands
metallacyclobutanes
Metathesis
Molybdenum
N-heterocyclic carbenes
olefin metathesis
Organic chemistry
Organometallic compounds
Reaction intermediates
Silica
Silicon dioxide
surface chemistry
olefin metathesis
surface chemistry
metallacyclobutanes
N-heterocyclic carbenes
molybdenum
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Summary: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 σ‐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. Mind the gap: Silica‐supported cationic Mo‐imido alkylidene complexes have been developed; these display unusual and contrasting catalytic metathesis activity for internal and terminal olefins, with a strong preference for the latter. The tailored ligand environment also allowed the first supported metallacyclobutane intermediate to be observed.
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ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201808233