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Highly Active and Thermally Robust Nickel Enolate Catalysts for the Synthesis of Ethylene‐Acrylate Copolymers

Xiong, Shuoyan and Hong, Alexandria and Bailey, Brad C. and Spinney, Heather A. and Senecal, Todd D. and Bailey, Hannah and Agapie, Theodor (2022) Highly Active and Thermally Robust Nickel Enolate Catalysts for the Synthesis of Ethylene‐Acrylate Copolymers. Angewandte Chemie International Edition . ISSN 1433-7851. doi:10.1002/anie.202206637. (In Press) https://resolver.caltech.edu/CaltechAUTHORS:20220720-917478000

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Abstract

The insertion copolymerization of polar olefins and ethylene remains a significant challenge in part due to catalysts′ low activity and poor thermal stability. Herein we demonstrate a strategy toward addressing these obstacles through ligand design. Neutral nickel phosphine enolate catalysts with large phosphine substituents reaching the axial positions of Ni achieve activity of up to 7.7×10³ kg mol⁻¹ h⁻¹ (efficiency >35×10³ g copolymer/g Ni) at 110 °C, notable for ethylene/acrylate copolymerization. NMR analysis of resulting copolymers reveals highly linear microstructures with main-chain ester functionality. Structure-performance studies indicate a strong correlation between axial steric hindrance and catalyst performance.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1002/anie.202206637DOIArticle
ORCID:
AuthorORCID
Xiong, Shuoyan0000-0002-2579-4260
Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2022 Wiley-VCH GmbH. Version of Record online: 18 July 2022. Accepted manuscript online: 20 June 2022. Manuscript received: 06 May 2022. We are grateful to Dow for funding (T.A.) and to the Caltech SURF program for a Ronan Armaan Mack fellowship (A.H.). We thank Jerzy Klosin, Alex Nett for insightful discussions. We thank Heidi Clements for GPC and tBA incorporation analysis. We thank Michael Takase for assistance with X-ray crystallography and David VanderVelde for assistance with NMR spectroscopy. Support has been provided for the X-ray diffraction and NMR instrumentation via the Dow Next Generation Educator Fund. S.X. acknowledge Manar Shoshani for assistance in refinement of solid-state structures and Yu Chen for assistance in generating topographical steric maps. Data Availability Statement. The data that support the findings of this study are available in the Supporting Information of this article. The authors declare no conflict of interest.
Funders:
Funding AgencyGrant Number
Caltech Summer Undergraduate Research Fellowship (SURF)UNSPECIFIED
Dow Next Generation Educator FundUNSPECIFIED
Subject Keywords:Acrylate; Catalysis; Copolymers; Nickel; Olefins
DOI:10.1002/anie.202206637
Record Number:CaltechAUTHORS:20220720-917478000
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220720-917478000
Official Citation:S. Xiong, A. Hong, B. C. Bailey, H. A. Spinney, T. D. Senecal, H. Bailey, T. Agapie, Angew. Chem. Int. Ed. 2022, e202206637; Angew. Chem. 2022, e202206637.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:115697
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:22 Jul 2022 17:22
Last Modified:22 Jul 2022 17:22

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