1196663-01-0Relevant academic research and scientific papers
Mechanistic studies on Ni(dppe)Cl2-catalyzed chain-growth polymerizations: Evidence for rate-determining reductive elimination
Lanni, Erica L.,McNeil, Anne J.
, p. 16573 - 16579 (2009)
The mechanisms for Ni(dppe)Cl2-catalyzed chain-growth polymerization of 4-bromo-2,5-bis-(hexyloxy)phenylmagnesium chloride and 5-bromo-4-hexylthiophen-2-ylmagnesium chloride were investigated. Rate studies utilizing IR spectroscopy and gas chromatography revealed that both polymerizations exhibit a first-order dependence on the catalyst concentration but a zeroth-order dependence on the monomer concentration. 31P NMR spectroscopic studies of the reactive organometallic intermediates suggest that the resting states are unsymmetrical NiII-biaryl and Ni II-bithiophene complexes. In combination, the data implicate reductive elimination as the rate-determining step for both monomers. Additionally, LiCl was found to have no effect on the rate-determining step or molecular weight distribution in the arene polymerization.
