Synthesis of Methylidene Complexes that Contain a 2,6-Dimesitylphenylimido Ligand and Ethenolysis of 2,3-Dicarbomethoxynorbornadiene

Monoalkoxide pyrrolide (MAP) complexes that contain a 2,6-dimesitylphenylimido (NAr*) ligand react with ethylene to yield unsubstituted metallacyclobutanes that are in equilibrium with methylidene complexes, W(NAr*)(CH2)(Me2Pyr)(OR) (R = t-Bu, OCMe(CF3)2, SiPh3, or 2,6-Me2C6H3). Polymerization of 2,...

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Published inOrganometallics Vol. 32; no. 19; pp. 5573 - 5580
Main Authors Gerber, Laura C. H, Schrock, Richard R
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 14.10.2013
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Inorganic & Nuclear
Chemistry, Organic
Physical Sciences
Science & Technology
ALKYLIDENE COMPLEXES
CROSS-METATHESIS
ENOL ETHERS
RING-OPENING/CROSS-METATHESIS
SELECTIVE OLEFIN METATHESIS
RUTHENIUM CATALYSTS
AROMATIC RING
PYRROLIDE MAP COMPLEXES
CLOSING METATHESIS
NORBORNENE DERIVATIVES
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Summary:Monoalkoxide pyrrolide (MAP) complexes that contain a 2,6-dimesitylphenylimido (NAr*) ligand react with ethylene to yield unsubstituted metallacyclobutanes that are in equilibrium with methylidene complexes, W(NAr*)(CH2)(Me2Pyr)(OR) (R = t-Bu, OCMe(CF3)2, SiPh3, or 2,6-Me2C6H3). Polymerization of 2,3-dicarbomethoxynorbornadiene (DCMNBD) with MCHCMe2Ph (M = Mo or W) initiators is slow as a consequence of a slow propagation step. However, W(NAr*)(CH2)(Me2Pyr)(OR) (R = SiPh3 or 2,6-dimethylphenyl) complexes react readily with 1 equiv of DCMNBD to give a monoinsertion product. The facile reaction between the monoinsertion product and ethylene then allows these complexes to be catalyts for the ring-opening cross-metathesis (ethenolysis) of DCMNBD and DCMNBE (2,3-dicarbomethoxynorbornene) with minimal formation of polymer.
ISSN:0276-7333
1520-6041
DOI:10.1021/om400844k