Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Tricoordinate Organochromium( III ) Complexes Supported by a Bulky Silylamido Ligand Produce Ultra‐High‐Molecular Weight Polyethylene in the Absence of Activators

Abstract

Low‐coordinate organoCr( III ) complexes supported by the silylamido ligand –N(SiMe 3 ) DIPP ( DIPP  = 2,6‐diisopropylphenyl) are ethylene polymerization catalyst precursors without the need of additional cocatalyst. The reaction of CrCl 3 ( THF ) 3 with 3 or 2 equiv. of LiN(SiMe 3 ) DIPP yields either a four‐membered cyclometalated Cr complex or Cr[N(SiMe 3 ) DIPP ] 2 Cl, respectively, with no trace of Cr[N(SiMe 3 ) DIPP ] 3 . Addition of 1 equiv. of LiN(SiMe 3 ) DIPP to Cr[N(SiMe 3 ) DIPP ] 2 Cl also leads to the four‐membered metallacycle, which upon heating transforms to a new six‐membered Cr metallacycle, likely via a σ ‐bond metathesis step. Cr[N(SiMe 3 ) DIPP ] 2 Cl can be readily converted to bis(amido)Cr( III ) vinyl and alkyl complexes Cr[N(SiMe 3 ) DIPP ] 2 R (R = vinyl, Bn, and Me). All of these structurally characterized low‐coordinate Cr( III ) complexes with a Cr–C bond initiate the polymerization of ethylene in the absence of activators or cocatalysts, producing ultra‐high‐molecular weight polyethylene.

Authors:
 [1];  [2];  [1];  [2];  [1];  [2]
+ Show Author Affiliations
  1. Department of Chemistry and Applied Biosciences ETH Zürich Vladimir‐Prelog‐Weg 2 CH‐8093 Zürich
  2. Department of Chemistry University of California, Berkeley Berkeley CA 94720‐1460 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1401003
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Helvetica Chimica Acta
Additional Journal Information:
Journal Name: Helvetica Chimica Acta Journal Volume: 99 Journal Issue: 11; Journal ID: ISSN 0018-019X
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Switzerland
Language:
English

Citation Formats

Liu, Hsueh‐Ju, Cai, Irene C., Fedorov, Alexey, Ziegler, Micah S., Copéret, Christophe, and Tilley, T. Don. Tricoordinate Organochromium( III ) Complexes Supported by a Bulky Silylamido Ligand Produce Ultra‐High‐Molecular Weight Polyethylene in the Absence of Activators. Switzerland: N. p., 2016. Web. doi:10.1002/hlca.201600199.
Copy to clipboard
Liu, Hsueh‐Ju, Cai, Irene C., Fedorov, Alexey, Ziegler, Micah S., Copéret, Christophe, & Tilley, T. Don. Tricoordinate Organochromium( III ) Complexes Supported by a Bulky Silylamido Ligand Produce Ultra‐High‐Molecular Weight Polyethylene in the Absence of Activators. Switzerland. https://doi.org/10.1002/hlca.201600199
Copy to clipboard
Liu, Hsueh‐Ju, Cai, Irene C., Fedorov, Alexey, Ziegler, Micah S., Copéret, Christophe, and Tilley, T. Don. Sat . "Tricoordinate Organochromium( III ) Complexes Supported by a Bulky Silylamido Ligand Produce Ultra‐High‐Molecular Weight Polyethylene in the Absence of Activators". Switzerland. https://doi.org/10.1002/hlca.201600199.
Copy to clipboard
@article{osti_1401003,
title = {Tricoordinate Organochromium( III ) Complexes Supported by a Bulky Silylamido Ligand Produce Ultra‐High‐Molecular Weight Polyethylene in the Absence of Activators},
author = {Liu, Hsueh‐Ju and Cai, Irene C. and Fedorov, Alexey and Ziegler, Micah S. and Copéret, Christophe and Tilley, T. Don},
abstractNote = {Low‐coordinate organoCr( III ) complexes supported by the silylamido ligand –N(SiMe 3 ) DIPP ( DIPP  = 2,6‐diisopropylphenyl) are ethylene polymerization catalyst precursors without the need of additional cocatalyst. The reaction of CrCl 3 ( THF ) 3 with 3 or 2 equiv. of LiN(SiMe 3 ) DIPP yields either a four‐membered cyclometalated Cr complex or Cr[N(SiMe 3 ) DIPP ] 2 Cl, respectively, with no trace of Cr[N(SiMe 3 ) DIPP ] 3 . Addition of 1 equiv. of LiN(SiMe 3 ) DIPP to Cr[N(SiMe 3 ) DIPP ] 2 Cl also leads to the four‐membered metallacycle, which upon heating transforms to a new six‐membered Cr metallacycle, likely via a σ ‐bond metathesis step. Cr[N(SiMe 3 ) DIPP ] 2 Cl can be readily converted to bis(amido)Cr( III ) vinyl and alkyl complexes Cr[N(SiMe 3 ) DIPP ] 2 R (R = vinyl, Bn, and Me). All of these structurally characterized low‐coordinate Cr( III ) complexes with a Cr–C bond initiate the polymerization of ethylene in the absence of activators or cocatalysts, producing ultra‐high‐molecular weight polyethylene.},
doi = {10.1002/hlca.201600199},
journal = {Helvetica Chimica Acta},
number = 11,
volume = 99,
place = {Switzerland},
year = {Sat Oct 08 00:00:00 EDT 2016},
month = {Sat Oct 08 00:00:00 EDT 2016}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Accepted Manuscript (Publisher)
Publisher's Version of Record
https://doi.org/10.1002/hlca.201600199
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Polymerization of Ethylene by Silica-Supported Dinuclear Cr III Sites through an Initiation Step Involving CH Bond Activation
journal, January 2014

  • Conley, Matthew P.; Delley, Murielle F.; Siddiqi, Georges
  • Angewandte Chemie International Edition, Vol. 53, Issue 7
  • DOI: 10.1002/anie.201308983

New software for searching the Cambridge Structural Database and visualizing crystal structures
journal, May 2002

  • Bruno, Ian J.; Cole, Jason C.; Edgington, Paul R.
  • Acta Crystallographica Section B Structural Science, Vol. 58, Issue 3
  • DOI: 10.1107/S0108768102003324

Paramagnetic alkylchromium compounds as homogeneous catalysts for the polymerization of ethylene
journal, January 1991

  • Thomas, Barbara J.; Noh, Seok Kyun; Schulte, Gayle K.
  • Journal of the American Chemical Society, Vol. 113, Issue 3
  • DOI: 10.1021/ja00003a024

Synthesis, Structure, and Magnetic and Electrochemical Properties of Quasi-Linear and Linear Iron(I), Cobalt(I), and Nickel(I) Amido Complexes
journal, August 2014

  • Lin, Chun-Yi; Fettinger, James C.; Grandjean, Fernande
  • Inorganic Chemistry, Vol. 53, Issue 17
  • DOI: 10.1021/ic501534f

Correlations Between Structure, Magnetism, and Polymerization Activity of Paramagnetic Benzylchromium Complexes
journal, June 1995

  • Bhandari, Gautam; Rheingold, Arnold L.; Theopold, Klaus H.
  • Chemistry - A European Journal, Vol. 1, Issue 3
  • DOI: 10.1002/chem.19950010309

Synthesis and reactivity of a conveniently prepared two-coordinate bis(amido) nickel(ii) complex
journal, January 2012

  • Lipschutz, Michael I.; Tilley, T. Don
  • Chemical Communications, Vol. 48, Issue 57
  • DOI: 10.1039/c2cc32974c

Reaction of 1-chloro-2-alkylcycloalkenes with organolithium reagents. A novel cyclopropanation reaction involving the generation of carbenes from vinyl halides
journal, October 1980

  • Gassman, Paul G.; Valcho, Joseph J.; Proehl, Gary S.
  • Journal of the American Chemical Society, Vol. 102, Issue 21
  • DOI: 10.1021/ja00541a022

Heterogeneity in the Distribution of Entanglement Density during Polymerization in Disentangled Ultrahigh Molecular Weight Polyethylene
journal, June 2011

  • Pandey, Anurag; Champouret, Yohan; Rastogi, Sanjay
  • Macromolecules, Vol. 44, Issue 12
  • DOI: 10.1021/ma2003689

Notes: Chromium Trichloride Tetrahydrofuranate
journal, September 1958

  • Herwig, W.; Zeiss, H.
  • The Journal of Organic Chemistry, Vol. 23, Issue 9
  • DOI: 10.1021/jo01103a627

Surface Chemistry and Spectroscopy of Chromium in Inorganic Oxides
journal, January 1996

  • Weckhuysen, Bert M.; Wachs, Israel E.; Schoonheydt, Robert A.
  • Chemical Reviews, Vol. 96, Issue 8
  • DOI: 10.1021/cr940044o

Constrained Geometry Chromium Catalysts for Olefin Polymerization
journal, January 1996

  • Liang, Yuanfeng; Yap, Glenn P. A.; Rheingold, Arnold L.
  • Organometallics, Vol. 15, Issue 25
  • DOI: 10.1021/om960774h

Homoleptic Two-Coordinate Silylamido Complexes of Chromium(I), Manganese(I), and Cobalt(I)
journal, December 2015

  • Werncke, C. Gunnar; Suturina, Elizaveta; Bunting, Philip C.
  • Chemistry - A European Journal, Vol. 22, Issue 5
  • DOI: 10.1002/chem.201503980

The Thermal Decomposition of Metal Alkyls in Hydrogen—Ethylene Mixtures
journal, March 1930

  • Taylor, Hugh S.; Jones, William H.
  • Journal of the American Chemical Society, Vol. 52, Issue 3
  • DOI: 10.1021/ja01366a044

Living Polymerization of Ethylene with a Titanium Complex Containing Two Phenoxy-Imine Chelate Ligands
journal, August 2001

A bis(amido) ligand set that supports two-coordinate chromium in the +1, +2, and +3 oxidation states
journal, January 2014

  • Cai, Irene C.; Lipschutz, Michael I.; Tilley, T. Don
  • Chem. Commun., Vol. 50, Issue 86
  • DOI: 10.1039/C4CC06615D

Structure and Reactivity of Trimethylsilylmethyl Complexes of Chromium, Including the 13-Electron Alkyl Cp*Cr(CH 2 SiMe 3 ) 2
journal, December 1998

  • Heintz, Robert A.; Leelasubcharoen, Somying; Liable-Sands, Louise M.
  • Organometallics, Vol. 17, Issue 25
  • DOI: 10.1021/om980796z

Synthesis, Characterization, and Alkyne Trimerization Catalysis of a Heteroleptic Two-Coordinate Fe I Complex
journal, May 2015

  • Lipschutz, Michael I.; Chantarojsiri, Teera; Dong, Yuyang
  • Journal of the American Chemical Society, Vol. 137, Issue 19
  • DOI: 10.1021/jacs.5b02504

Olefin polymerization over supported chromium oxide catalysts
journal, June 1999

Advances in Non-Metallocene Olefin Polymerization Catalysis
journal, January 2003

  • Gibson, Vernon C.; Spitzmesser, Stefan K.
  • Chemical Reviews, Vol. 103, Issue 1
  • DOI: 10.1021/cr980461r

Living Polymerization of Ethylene Catalyzed by Titanium Complexes Having Fluorine-Containing Phenoxy−Imine Chelate Ligands
journal, April 2002

  • Mitani, Makoto; Mohri, Jun-ichi; Yoshida, Yasunori
  • Journal of the American Chemical Society, Vol. 124, Issue 13
  • DOI: 10.1021/ja0117581

The Search for New-Generation Olefin Polymerization Catalysts: Life beyond Metallocenes
journal, February 1999

Paramagnetic (Benzyl)chromium Complexes as Homogeneous Ethylene Polymerization Catalysts
journal, February 1995

  • Bhandari, Gautam; Kim, Youhyuk; McFarland, Jeffrey M.
  • Organometallics, Vol. 14, Issue 2
  • DOI: 10.1021/om00002a023

Proton transfers are key elementary steps in ethylene polymerization on isolated chromium(III) silicates
journal, July 2014

  • Delley, M. F.; Nunez-Zarur, F.; Conley, M. P.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 32
  • DOI: 10.1073/pnas.1405314111

Performance of the Cr[CH(SiMe3)2]3/SiO2 catalyst for ethylene polymerization compared with the performance of the Phillips catalyst
journal, December 2002

  • Ikeda, Haruhiko; Monoi, Takashi; Sasaki, Yasuaki
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 41, Issue 3
  • DOI: 10.1002/pola.10590

Preparation and Characterization of a Reduced Chromium Complex via Vinyl Oxidative Coupling: Formation of a Self-Activating Catalyst for Selective Ethylene Trimerization
journal, April 2011

  • Albahily, Khalid; Fomitcheva, Valeria; Gambarotta, Sandro
  • Journal of the American Chemical Society, Vol. 133, Issue 16
  • DOI: 10.1021/ja200593k

The Chemistry of 1,3,5-Triazacyclohexane Complexes, 3. High Yield Synthesis of [Cr{N(SiMe3)2}3] and Accurate Structure Determination by Cocrystallization with Me6Si2
journal, January 1996

  • Köhn, Randolf D.; Kociok-Köhn, Gabriele; Haufe, Matthias
  • Chemische Berichte, Vol. 129, Issue 1
  • DOI: 10.1002/cber.19961290107

A Chromium Catalyst for the Polymerization of Ethylene as a Homogeneous Model for the Phillips Catalyst
journal, February 2005

  • MacAdams, Leonard A.; Buffone, Gerald P.; Incarvito, Christopher D.
  • Journal of the American Chemical Society, Vol. 127, Issue 4
  • DOI: 10.1021/ja043877x

α-Olefin Polymerization with Ether-Coordinated Chromium(III) Alkyls
journal, January 1996

  • White, Paul A.; Calabrese, Joe; Theopold, Klaus H.
  • Organometallics, Vol. 15, Issue 26
  • DOI: 10.1021/om960697q

A Structurally Rigid Bis(amido) Ligand Framework in Low-Coordinate Ni(I), Ni(II), and Ni(III) Analogues Provides Access to a Ni(III) Methyl Complex via Oxidative Addition
journal, October 2013

  • Lipschutz, Michael I.; Yang, Xinzheng; Chatterjee, Ruchira
  • Journal of the American Chemical Society, Vol. 135, Issue 41
  • DOI: 10.1021/ja408151h

Molar Mass and Molecular Weight Distribution Determination Of UHMWPE Synthesized Using a Living Homogeneous Catalyst
journal, March 2010

  • Talebi, Saeid; Duchateau, Rob; Rastogi, Sanjay
  • Macromolecules, Vol. 43, Issue 6
  • DOI: 10.1021/ma902297b

Heterolytic Activation of C–H Bonds on Cr III –O Surface Sites Is a Key Step in Catalytic Polymerization of Ethylene and Dehydrogenation of Propane
journal, March 2015

  • Conley, Matthew P.; Delley, Murielle F.; Núñez-Zarur, Francisco
  • Inorganic Chemistry, Vol. 54, Issue 11
  • DOI: 10.1021/ic502696n

Cationic chromium(III) alkyls as olefin polymerization catalysts
journal, August 1988

  • Thomas, Barbara J.; Theopold, Klaus H.
  • Journal of the American Chemical Society, Vol. 110, Issue 17
  • DOI: 10.1021/ja00225a053

Preparation, Characterization and Crystal Structure of the Dinuclear Chromium Complex {(C5H5)Cr[μ-CH2SiMe2−N(SiMe3)]}2
journal, June 2000

Ethylene Polymerization with Silica-Supported Cr[CH(SiMe3)2]3 Catalyst. Effect of Silica Calcination Temperature and Cr Content
journal, January 2003

  • Monoi, Takashi; Ikeda, Haruhiko; Sasaki, Yasuaki
  • Polymer Journal, Vol. 35, Issue 7
  • DOI: 10.1295/polymj.35.608

The First Structural Characterisation of a Group 2 Metal Alkylperoxide Complex: Comments on the Cleavage of Dioxygen by Magnesium Alkyl Complexes
journal, October 2003

  • Bailey, Philip J.; Coxall, Robert A.; Dick, Caroline M.
  • Chemistry - A European Journal, Vol. 9, Issue 19
  • DOI: 10.1002/chem.200305053

Bulk susceptibility corrections in nuclear magnetic resonance experiments using superconducting solenoids
journal, June 1970

  • Live, David H.; Chan, Sunney I.
  • Analytical Chemistry, Vol. 42, Issue 7
  • DOI: 10.1021/ac60289a028

The (Ph) 2 nacnac Ligand in Organochromium Chemistry
journal, March 2002

  • MacAdams, Leonard A.; Kim, Woo-Kyu; Liable-Sands, Louise M.
  • Organometallics, Vol. 21, Issue 5
  • DOI: 10.1021/om010857k

C—H Bond Activation in Transition Metal Species from a Computational Perspective
journal, February 2010

  • Balcells, David; Clot, Eric; Eisenstein, Odile
  • Chemical Reviews, Vol. 110, Issue 2
  • DOI: 10.1021/cr900315k

Mechanism of Initiation in the Phillips Ethylene Polymerization Catalyst: Redox Processes Leading to the Active Site
journal, August 2015

The Cambridge Structural Database: a quarter of a million crystal structures and rising
journal, May 2002

Homogeneous Chromium Catalysts for Olefin Polymerization
book, March 1992

Poisoning studies on chromium/silica. 2. Carbon monoxide
journal, April 1991

  • McDaniel, M. P.; Martin, S. J.
  • The Journal of Physical Chemistry, Vol. 95, Issue 8
  • DOI: 10.1021/j100161a059

How to Polymerize Ethylene in a Highly Controlled Fashion?
journal, March 2007

Preparation and properties of tantalum imido complexes and their reactions with alkynes. Coordination control through multiple metal-ligand bonding
journal, October 1989

  • Chao, Yuan Wei; Wexler, Pamela A.; Wigley, David E.
  • Inorganic Chemistry, Vol. 28, Issue 20
  • DOI: 10.1021/ic00319a022

Computational Kinetic Discrimination of Ethylene Polymerization Mechanisms for the Phillips (Cr/SiO 2 ) Catalyst
journal, May 2015

Homogeneous Chromium Catalysts for Olefin Polymerization
journal, January 1998

    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: