2,4,6–Triphenylpyridinium: A Bulky, Highly Electron–Withdrawing Substituent Which Enhances Properties of Nickel(II) Ethylene Polymerization Catalysts

Daugulis, Olafs; Brookhart, Maurice; Janeta, Mateusz; Heidlas, Julius X.

doi:10.1002/anie.202013854

Title: 2,4,6–Triphenylpyridinium: A Bulky, Highly Electron–Withdrawing Substituent Which Enhances Properties of Nickel(II) Ethylene Polymerization Catalysts

Journal Article · Mon Nov 23 00:00:00 EST 2020 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202013854· OSTI ID:1755772

Daugulis, Olafs ^[1]; Brookhart, Maurice ^[1]; Janeta, Mateusz ^[1]; Heidlas, Julius X. ^[1]

Univ. of Houston, TX (United States)

Abstract The reactivity of Ni ^II and Pd ^II olefin polymerization catalysts can be enhanced by introduction of electron‐withdrawing substituents on the supporting ligands rendering the metal centers more electrophilic. Reported here is a comparison of ethylene polymerization activity of a classical salicyliminato nickel catalyst substituted with the powerful electron‐withdrawing 2,4,6‐triphenylpyridinium (trippy) group to the ‐CF ₃ analogue. The trippy substituent is substantially more electron‐withdrawing (σ _meta =0.63) than the trifluoromethyl group (σ _meta =0.43) which results in a ca. 8‐fold increase in catalytic turnover frequency. An additional advantage of trippy is the high steric bulk relative to the trifluoromethyl group. This feature results in a four‐fold increase in polymer molecular weight owing to enhanced retardation of chain transfer. A significant increase in catalyst lifetime is observed as well.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Univ. of Houston, TX (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Welch Foundation

Grant/Contract Number:: SC0021403; H-E-0041

OSTI ID:: 1755772

Alternate ID(s):: OSTI ID: 1786185

Journal Information:: Angewandte Chemie (International Edition), Vol. 60, Issue 9; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (46)

New Pd(II)- and Ni(II)-Based Catalysts for Polymerization of Ethylene and .alpha.-Olefins Johnson, Lynda K.; Killian, Christopher M.; Brookhart, Maurice Journal of the American Chemical Society, Vol. 117, Issue 23 https://doi.org/10.1021/ja00128a054	journal	June 1995
Late-Metal Catalysts for Ethylene Homo- and Copolymerization Ittel, Steven D.; Johnson, Lynda K.; Brookhart, Maurice Chemical Reviews, Vol. 100, Issue 4 https://doi.org/10.1021/cr9804644	journal	April 2000
Synthesis of Semicrystalline Polyolefin Materials: Precision Methyl Branching via Stereoretentive Chain Walking Vaccarello, David N.; O’Connor, Kyle S.; Iacono, Pasquale Journal of the American Chemical Society, Vol. 140, Issue 20 https://doi.org/10.1021/jacs.8b02963	journal	April 2018
(α-Diimine)nickel Complexes That Contain Menthyl Substituents: Synthesis, Conformational Behavior, and Olefin Polymerization Catalysis Zhai, Feng; Jordan, Richard F. Organometallics, Vol. 36, Issue 15 https://doi.org/10.1021/acs.organomet.7b00283	journal	July 2017
Coordination−Insertion Copolymerization of Fundamental Polar Monomers Nakamura, Akifumi; Ito, Shingo; Nozaki, Kyoko Chemical Reviews, Vol. 109, Issue 11 https://doi.org/10.1021/cr900079r	journal	November 2009
Designing catalysts for olefin polymerization and copolymerization: beyond electronic and steric tuning Chen, Changle Nature Reviews Chemistry, Vol. 2, Issue 5 https://doi.org/10.1038/s41570-018-0003-0	journal	April 2018
Recent developments in redox-active olefin polymerization catalysts Kaiser, Jordan M.; Long, Brian K. Coordination Chemistry Reviews, Vol. 372 https://doi.org/10.1016/j.ccr.2018.06.007	journal	October 2018
Semi-Crystalline Polar Polyethylene: Ester-Functionalized Linear Polyolefins Enabled by a Functional-Group-Tolerant, Cationic Nickel Catalyst Long, Brian K.; Eagan, James M.; Mulzer, Michael Angewandte Chemie International Edition, Vol. 55, Issue 25 https://doi.org/10.1002/anie.201601703	journal	May 2016
Semi-Crystalline Polar Polyethylene: Ester-Functionalized Linear Polyolefins Enabled by a Functional-Group-Tolerant, Cationic Nickel Catalyst Long, Brian K.; Eagan, James M.; Mulzer, Michael Angewandte Chemie, Vol. 128, Issue 25 https://doi.org/10.1002/ange.201601703	journal	May 2016
Ultrahigh Branching of Main‐Chain‐Functionalized Polyethylenes by Inverted Insertion Selectivity Zhang, Yuxing; Wang, Chaoqun; Mecking, Stefan Angewandte Chemie International Edition, Vol. 59, Issue 34 https://doi.org/10.1002/anie.202004763	journal	July 2020
Ultrahigh Branching of Main‐Chain‐Functionalized Polyethylenes by Inverted Insertion Selectivity Zhang, Yuxing; Wang, Chaoqun; Mecking, Stefan Angewandte Chemie, Vol. 132, Issue 34 https://doi.org/10.1002/ange.202004763	journal	July 2020
Electron-Rich Metal Cations Enable Synthesis of High Molecular Weight, Linear Functional Polyethylenes Zhang, Wei; Waddell, Peter M.; Tiedemann, Margaret A. Journal of the American Chemical Society, Vol. 140, Issue 28 https://doi.org/10.1021/jacs.8b04712	journal	June 2018
Allosteric Effects in Ethylene Polymerization Catalysis. Enhancement of Performance of Phosphine-Phosphinate and Phosphine-Phosphonate Palladium Alkyl Catalysts by Remote Binding of B(C ₆ F ₅ ) ₃ Wilders, Alison M.; Contrella, Nathan D.; Sampson, Jessica R. Organometallics, Vol. 36, Issue 24 https://doi.org/10.1021/acs.organomet.7b00815	journal	November 2017
Copolymerization of Nonpolar Olefins and Allyl Acetate Using Nickel Catalysts Bearing a Methylene-Bridged Bisphosphine Monoxide Ligand Jung, Jin; Yasuda, Hina; Nozaki, Kyoko Macromolecules, Vol. 53, Issue 7 https://doi.org/10.1021/acs.macromol.0c00183	journal	April 2020
Neutral Nickel Catalysts for Olefin Homo- and Copolymerization: Relationships between Catalyst Structures and Catalytic Properties Mu, Hongliang; Pan, Li; Song, Dongpo Chemical Reviews, Vol. 115, Issue 22 https://doi.org/10.1021/cr500370f	journal	November 2015
Ortho -Phosphinobenzenesulfonate: A Superb Ligand for Palladium-Catalyzed Coordination–Insertion Copolymerization of Polar Vinyl Monomers Nakamura, Akifumi; Anselment, Timo M. J.; Claverie, Jerome Accounts of Chemical Research, Vol. 46, Issue 7 https://doi.org/10.1021/ar300256h	journal	April 2013
Rational Design of High-Performance Phosphine Sulfonate Nickel Catalysts for Ethylene Polymerization and Copolymerization with Polar Monomers Chen, Min; Chen, Changle ACS Catalysis, Vol. 7, Issue 2 https://doi.org/10.1021/acscatal.6b03394	journal	January 2017
Copolymerization of Vinyl Acetate with Ethylene by Palladium/Alkylphosphine−Sulfonate Catalysts Ito, Shingo; Munakata, Kagehiro; Nakamura, Akifumi Journal of the American Chemical Society, Vol. 131, Issue 41 https://doi.org/10.1021/ja9050839	journal	September 2009
Formation of Linear Copolymers of Ethylene and Acrylonitrile Catalyzed by Phosphine Sulfonate Palladium Complexes Kochi, Takuya; Noda, Shusuke; Yoshimura, Kenji Journal of the American Chemical Society, Vol. 129, Issue 29 https://doi.org/10.1021/ja0725504	journal	July 2007
Palladium catalysed copolymerisation of ethene with alkylacrylates: polar comonomer built into the linear polymer chainElectronic supplementary information (ESI) available: NMR data for entries 1, 9, 10, 12 and size exclusion chromatographic data for entries 1, 3, 8, 12. See http://www.rsc.org/suppdata/cc/b1/b111252j/ Drent, Eite; van Dijk, Rudmer; van Ginkel, Roel Chemical Communications, Issue 7 https://doi.org/10.1039/b111252j	journal	March 2002
Neutral Nickel(II)-Based Catalysts for Ethylene Polymerization Wang, Chunming; Friedrich, Stefan; Younkin, Todd R. Organometallics, Vol. 17, Issue 15 https://doi.org/10.1021/om980176y	journal	July 1998
Neutral, Single-Component Nickel (II) Polyolefin Catalysts That Tolerate Heteroatoms Younkin, T. R. Science, Vol. 287, Issue 5452 https://doi.org/10.1126/science.287.5452.460	journal	January 2000
Linear functionalized polyethylene prepared with highly active neutral Ni(II) complexes Connor, Eric F.; Younkin, Todd R.; Henderson, Jason I. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 40, Issue 16 https://doi.org/10.1002/pola.10370	journal	August 2002
Synthesis of neutral nickel catalysts for ethylene polymerization ? the influence of ligand size on catalyst stabilityElectronic supplementary information (ESI) available: experimental protocol for (tmeda)Ni(Me)2 and compounds 3,4,7,8,9 and 10 and 1H-NMR magnetization transfer data for compound 7. See http://www.rsc.org/suppdata/cc/b3/b306701g/ Connor, Eric F.; Younkin, Todd R.; Henderson, Jason I. Chemical Communications, Issue 18 https://doi.org/10.1039/b306701g	journal	January 2003
Remote Perfluoroalkyl Substituents are Key to Living Aqueous Ethylene Polymerization Schnitte, Manuel; Scholliers, Janine S.; Riedmiller, Kai Angewandte Chemie International Edition, Vol. 59, Issue 8 https://doi.org/10.1002/anie.201913117	journal	February 2020
Remote Perfluoroalkyl Substituents are Key to Living Aqueous Ethylene Polymerization Schnitte, Manuel; Scholliers, Janine S.; Riedmiller, Kai Angewandte Chemie, Vol. 132, Issue 8 https://doi.org/10.1002/ange.201913117	journal	January 2020
Controlled Polymerization in Polar Solvents to Ultrahigh Molecular Weight Polyethylene Kenyon, Philip; Wörner, Melissa; Mecking, Stefan Journal of the American Chemical Society, Vol. 140, Issue 21 https://doi.org/10.1021/jacs.8b03223	journal	May 2018
Pentafluorophenyl Groups as Remote Substituents in Ni(II) Polymerization Catalysis Schnitte, Manuel; Lipinski, Sophia; Schiebel, Eva Organometallics, Vol. 39, Issue 1 https://doi.org/10.1021/acs.organomet.9b00784	journal	December 2019
Ligand Steric and Electronic Effects on β-Ketiminato Neutral Nickel(II) Olefin Polymerization Catalysts Song, Dong-Po; Shi, Xin-Cui; Wang, Yong-Xia Organometallics, Vol. 31, Issue 3 https://doi.org/10.1021/om2010194	journal	January 2012
Highly Active Single-Component Neutral Nickel Ethylene Polymerization Catalysts: The Influence of Electronic Effects and Spectator Ligands Mu, Hong-Liang; Ye, Wei-Ping; Song, Dong-Po Organometallics, Vol. 29, Issue 23 https://doi.org/10.1021/om100658j	journal	December 2010
Substituent Effects in (κ ² - N , O )-Salicylaldiminato Nickel(II)−Methyl Pyridine Polymerization Catalysts: Terphenyls Controlling Polyethylene Microstructures Göttker-Schnetmann, Inigo; Wehrmann, Peter; Röhr, Caroline Organometallics, Vol. 26, Issue 9 https://doi.org/10.1021/om0611498	journal	April 2007
Control of Chain Walking by Weak Neighboring Group Interactions in Unsymmetrical Catalysts Falivene, Laura; Wiedemann, Thomas; Göttker-Schnetmann, Inigo Journal of the American Chemical Society, Vol. 140, Issue 4 https://doi.org/10.1021/jacs.7b08975	journal	January 2018
Remote Substituents Controlling Catalytic Polymerization by Very Active and Robust Neutral Nickel(II) Complexes Zuideveld, Martin A.; Wehrmann, Peter; Röhr, Caroline Angewandte Chemie International Edition, Vol. 43, Issue 7 https://doi.org/10.1002/anie.200352062	journal	February 2004
Remote Substituents Controlling Catalytic Polymerization by Very Active and Robust Neutral Nickel(II) Complexes Zuideveld, Martin A.; Wehrmann, Peter; Röhr, Caroline Angewandte Chemie, Vol. 116, Issue 7 https://doi.org/10.1002/ange.200352062	journal	February 2004
Nickel Catalyzed Copolymerization of Ethylene and Alkyl Acrylates Xin, Bruce S.; Sato, Naomasa; Tanna, Akio Journal of the American Chemical Society, Vol. 139, Issue 10 https://doi.org/10.1021/jacs.6b13051	journal	March 2017
Robust Bulky [P,O] Neutral Nickel Catalysts for Copolymerization of Ethylene with Polar Vinyl Monomers Zhang, Yanping; Mu, Hongliang; Pan, Li ACS Catalysis, Vol. 8, Issue 7 https://doi.org/10.1021/acscatal.8b01088	journal	May 2018
Synthesis and Ethylene Polymerization Activity of a Series of 2-Anilinotropone-Based Neutral Nickel(II) Catalysts Hicks, Frederick A.; Jenkins, Jason C.; Brookhart, Maurice Organometallics, Vol. 22, Issue 17 https://doi.org/10.1021/om030142c	journal	August 2003
New Neutral Nickel and Palladium Sandwich Catalysts: Synthesis of Ultra-High Molecular Weight Polyethylene (UHMWPE) via Highly Controlled Polymerization and Mechanistic Studies of Chain Propagation Tran, Quan H.; Brookhart, Maurice; Daugulis, Olafs Journal of the American Chemical Society, Vol. 142, Issue 15 https://doi.org/10.1021/jacs.0c02045	journal	April 2020
A Mechanistic Investigation of the Polymerization of Ethylene Catalyzed by Neutral Ni(II) Complexes Derived from Bulky Anilinotropone Ligands Jenkins, Jason C.; Brookhart, Maurice Journal of the American Chemical Society, Vol. 126, Issue 18 https://doi.org/10.1021/ja030634g	journal	May 2004
Synthesis, Characterization, and Ethylene Polymerization Activities of Neutral Nickel(II) Complexes Derived from Anilino-Substituted Enone Ligands Bearing Trifluoromethyl and Trifluoroacetyl Substituents Zhang, Lei; Brookhart, Maurice; White, Peter S. Organometallics, Vol. 25, Issue 8 https://doi.org/10.1021/om050931p	journal	March 2006
Synthesis of Branched Ultrahigh-Molecular-Weight Polyethylene Using Highly Active Neutral, Single-Component Ni(II) Catalysts Chen, Zhou; Mesgar, Milad; White, Peter S. ACS Catalysis, Vol. 5, Issue 2 https://doi.org/10.1021/cs501948d	journal	December 2014
Pentafluorosulfanyl Substituents in Polymerization Catalysis Kenyon, Philip; Mecking, Stefan Journal of the American Chemical Society, Vol. 139, Issue 39 https://doi.org/10.1021/jacs.7b06745	journal	September 2017
A survey of Hammett substituent constants and resonance and field parameters Hansch, Corwin.; Leo, A.; Taft, R. W. Chemical Reviews, Vol. 91, Issue 2 https://doi.org/10.1021/cr00002a004	journal	March 1991
Properties of the amino group in N-(aminophenyl)pyridinium perchlorates Dorofeenko, G. N.; Andreichikov, Yu. P.; Zvezdina, �. A. Chemistry of Heterocyclic Compounds, Vol. 10, Issue 10 https://doi.org/10.1007/BF00470158	journal	October 1974
Deactivation Pathways of Neutral Ni(II) Polymerization Catalysts Berkefeld, Andreas; Mecking, Stefan Journal of the American Chemical Society, Vol. 131, Issue 4 https://doi.org/10.1021/ja808855v	journal	February 2009
Well-defined phosphino-phenolate neutral nickel( ii ) catalysts for efficient (co)polymerization of norbornene and ethylene Zhang, Yan-Ping; Li, Wei-Wei; Li, Bai-Xiang Dalton Transactions, Vol. 44, Issue 16 https://doi.org/10.1039/C5DT00074B	journal	January 2015

Linked Research (3)

Similar Records

2,4,6‐Triphenylpyridinium: A Bulky, Highly Electron‐Withdrawing Substituent That Enhances Properties of Nickel(II) Ethylene Polymerization Catalysts

Journal Article · Wed Jan 20 00:00:00 EST 2021 · Angewandte Chemie · OSTI ID:1755772

Janeta, Mateusz; Heidlas, Julius X.; Daugulis, Olafs; +1 more

Polymerization of Terminal Acetylenes by a Bulky Monophosphine-Palladium Catalyst

Journal Article · Mon Jan 23 00:00:00 EST 2023 · Organometallics · OSTI ID:1755772

Chen, Zhi-Hao; Daugulis, Olafs; Brookhart, Maurice

IMIDAZOLE-BASED IONIC LIQUIDS FOR USE IN POLYMER ELECTROLYTE MEMBRANE FUEL CELLS: EFFECT OF ELECTRON-WITHDRAWING AND ELECTRON-DONATING SUBSTITUENTS

Journal Article · Thu Jan 01 00:00:00 EST 2009 · Journal of Undergraduate Research · OSTI ID:1755772

Chang, E; Fu, Y; Kerr, J

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Ethylene
polymerization
polyolefins
late transition metal catalysis
nickel
homogeneous catalysis
ligand design

CCDC 2003990: Experimental Crystal Structure Determination Mateusz, Janeta,; X., Heidlas, Julius; Olafs, Daugulis, https://doi.org/10.5517/ccdc.csd.cc2589vm The current record is supplemented by this dataset	dataset	January 2021
CCDC 2008412: Experimental Crystal Structure Determination Mateusz, Janeta,; X., Heidlas, Julius; Olafs, Daugulis, https://doi.org/10.5517/ccdc.csd.cc25dxh0 The current record is supplemented by this dataset	dataset	January 2021
CCDC 2008414: Experimental Crystal Structure Determination Mateusz, Janeta,; X., Heidlas, Julius; Olafs, Daugulis, https://doi.org/10.5517/ccdc.csd.cc25dxk2 The current record is supplemented by this dataset	dataset	January 2021

Title: 2,4,6–Triphenylpyridinium: A Bulky, Highly Electron–Withdrawing Substituent Which Enhances Properties of Nickel(II) Ethylene Polymerization Catalysts

Citation Formats

References (46)

Linked Research (3)

Similar Records

Related Subjects