Evidence for Ligand-Dependent Mechanistic Changes in Nickel-Catalyzed Chain-Growth Polymerizations

Autor:	Anne J. McNeil, Erica L. Lanni
Rok vydání:	2010
Předmět:	Reaction mechanism Polymers and Plastics Organic Chemistry Grignard reaction Chloride Catalysis Inorganic Chemistry chemistry.chemical_compound Transmetalation Monomer chemistry Catalytic cycle Polymerization Polymer chemistry Materials Chemistry medicine medicine.drug
Zdroj:	Macromolecules. 43:8039-8044
ISSN:	1520-5835 0024-9297
Popis:	The mechanisms for Ni(dppp)Cl2-catalyzed chain-growth polymerization of 4-bromo-2,5-bis(hexyloxy)phenylmagnesium chloride and 5-bromo-4-hexylthiophen-2-ylmagnesium chloride were investigated. A combination of rate and spectroscopic studies revealed that transmetalation is the rate-determining step of the catalytic cycle for both monomers. 31P NMR spectroscopic studies revealed that a Ni(II)−aryl halide and a Ni(II)−thienyl halide are the catalyst resting states. In addition, LiCl was found to alter the arene polymerization rates. These results are different than those previously obtained with an alternative catalyst (Ni(dppe)Cl2) and suggest that the ligand has a strong mechanistic influence on the polymerization.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::160d518e25ee1247578d773427ee8cdf https://doi.org/10.1021/ma101565u Zobrazit plný text záznamu