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Mechanistic studies of P,O-chelated nickel complexes targeting functional polyolefin synthesis

Xiong, Shuoyan and Shoshani, Manar M. and Zhang, Xinglong and Spinney, Heather A. and Nett, Alex J. and Henderson, Briana S. and Miller, Thomas F., III and Agapie, Theodor (2022) Mechanistic studies of P,O-chelated nickel complexes targeting functional polyolefin synthesis. In: 258th ACS National Meeting & Exposition, March 20-24, 2022, San Diego, CA.

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The efficient copolymerization of ethylene with functionalized olefins using Ni catalysts remains a challenge. Herein, we report two neutral Ni(II) catalysts that exhibit high thermal stability and significantly higher incorporation of acrylates or improved resistance to acrylate-induced chain transfer, in comparison to previously reported catalysts. Nickel alkyl complexes generated after tBA insertion were isolated and, for the first time, characterized by crystallography. 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 acrylate insertion is the rate limiting step of copolymerization.

Item Type:Conference or Workshop Item (Paper)
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URLURL TypeDescription presentation abstract, ACS Spring 2022
Xiong, Shuoyan0000-0002-2579-4260
Shoshani, Manar M.0000-0002-4051-3367
Zhang, Xinglong0000-0003-1698-692X
Miller, Thomas F., III0000-0002-1882-5380
Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2022 American Chemical Society.
Record Number:CaltechAUTHORS:20220714-215129425
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:115588
Deposited By: Shuoyan Xiong
Deposited On:15 Jul 2022 22:51
Last Modified:15 Jul 2022 22:51

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