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Promoting Terminal Olefin Metathesis with a Supported Cationic Molybdenum Imido Alkylidene N‐Heterocyclic Carbene Catalyst
Author(s) -
Pucino Margherita,
Inoue Mariko,
Gordon Christopher P.,
Schowner Roman,
Stöhr Laura,
Sen Suman,
Hegedüs Csaba,
Robé Emmanuel,
Tóth Flórián,
Buchmeiser Michael R.,
Copéret Christophe
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201808233
Subject(s) - carbene , cationic polymerization , metathesis , chemistry , catalysis , salt metathesis reaction , acyclic diene metathesis , ligand (biochemistry) , ring opening metathesis polymerisation , medicinal chemistry , olefin metathesis , ethylene , polymer chemistry , organic chemistry , polymerization , biochemistry , polymer , receptor
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.