We have located links that may give you full text access.
Efficient Copolymerization of Acrylate and Ethylene with Neutral P, O-Chelated Nickel Catalysts: Mechanistic Investigations of Monomer Insertion and Chelate Formation.
Journal of the American Chemical Society 2021 April 23
The efficient copolymerization of acrylates with ethylene using Ni catalysts remains a challenge. Herein, we report two neutral Ni(II) catalysts (POP-Ni-py ( 1 ) and PONap-Ni-py ( 2 )) that exhibit high thermal stability and significantly higher incorporation of polar monomer (for 1 ) or improved resistance to tert -butylacrylate (tBA)-induced chain transfer (for 2 ), in comparison to previously reported catalysts. Nickel alkyl complexes generated after tBA insertion, POP-Ni-CCO(py) ( 3 ) and PONap-Ni-CCO(py) ( 4 ), were isolated and, for the first time, characterized by crystallography. Weakened lutidine vs pyridine coordination in 2- lut facilitated the isolation of a N-donor-free adduct after acrylate insertion PONap-Ni-CCO ( 5 ) which represents a novel example of a four-membered chelate relevant to acrylate polymerization catalysis. Experimental kinetic studies of six cases of monomer insertion with aforementioned nickel complexes indicate that pyridine dissociation and monomer coordination are fast relative to monomer migratory insertion and that monomer enchainment after tBA insertion is the rate limiting step of copolymerization. Further evaluation of monomer insertion using density functional theory studies identified a cis-trans isomerization via Berry-pseudorotation involving one of the pendant ether groups as the rate-limiting step for propagation, in the absence of a polar group at the chain end. The energy profiles for ethylene and tBA enchainments are in qualitative agreement with experimental measurements.
Full text links
Related Resources
Trending Papers
Get seemless 1-tap access through your institution/university
For the best experience, use the Read mobile app
All material on this website is protected by copyright, Copyright © 1994-2024 by WebMD LLC.
This website also contains material copyrighted by 3rd parties.
By using this service, you agree to our terms of use and privacy policy.
Your Privacy Choices
You can now claim free CME credits for this literature searchClaim now
Get seemless 1-tap access through your institution/university
For the best experience, use the Read mobile app