Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators

Autenrieth, Benjamin; Schrock, Richard R.

doi:10.1021/acs.macromol.5b00161

Title: Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators

Abstract

Here we report the synthesis of >98% cis,isotactic and cis,syndiotactic polynorbornene (poly(NBE)) and poly(endo,anti-tetracyclododecene) (poly(TCD)). Cis,isotactic poly(NBE) and poly(TCD) were prepared employing Mo-based biphenolate imido alkylidene initiators, Mo(NR)(CHCMe₂Ph)(Biphen) (Biphen = e.g., 3,3'-(t-Bu)2-5,5'-6,6'-(CH₃)4-1,1'-biphenyl-2,2'-diolate), while cis,syndiotactic poly(NBE) and poly(TCD) were prepared employing W-based imido or oxo monoaryloxide pyrrolide (MAP) initiators, W(X)(CHR')(Pyrrolide)(OTer) (X = NR or O; OTer = a 2,6-terphenoxide). Addition of 1-hexene or coordinating solvents such as THF do not decrease the stereospecificity of the polymerization. Cis,iso and cis,syndio dyads can be distinguished through investigation of ¹H and ¹³C NMR spectra of the two polymers in a mixture. The polymers were hydrogenated to give isotactic and syndiotactic H-poly(NBE) and H-poly(TCD).

Authors:

Autenrieth, Benjamin ^[1]; Schrock, Richard R. ^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Publication Date:: Tue Apr 07 00:00:00 EDT 2015

Research Org.:: Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1557800

Grant/Contract Number:: FG02-86ER13564

Resource Type:: Accepted Manuscript

Journal Name:: Macromolecules

Additional Journal Information:: Journal Volume: 48; Journal Issue: 8; Journal ID: ISSN 0024-9297

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Autenrieth, Benjamin, and Schrock, Richard R. Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators.  United States: N. p., 2015. 
Web.  doi:10.1021/acs.macromol.5b00161.

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                    Autenrieth, Benjamin, & Schrock, Richard R. Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators.  United States.  https://doi.org/10.1021/acs.macromol.5b00161

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                    Autenrieth, Benjamin, and Schrock, Richard R. Tue .  
"Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators".  United States.  https://doi.org/10.1021/acs.macromol.5b00161.  https://www.osti.gov/servlets/purl/1557800.

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@article{osti_1557800,

  title        = {Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators},

  author       = {Autenrieth, Benjamin and Schrock, Richard R.},

  abstractNote = {Here we report the synthesis of >98% cis,isotactic and cis,syndiotactic polynorbornene (poly(NBE)) and poly(endo,anti-tetracyclododecene) (poly(TCD)). Cis,isotactic poly(NBE) and poly(TCD) were prepared employing Mo-based biphenolate imido alkylidene initiators, Mo(NR)(CHCMe2Ph)(Biphen) (Biphen = e.g., 3,3'-(t-Bu)2-5,5'-6,6'-(CH3)4-1,1'-biphenyl-2,2'-diolate), while cis,syndiotactic poly(NBE) and poly(TCD) were prepared employing W-based imido or oxo monoaryloxide pyrrolide (MAP) initiators, W(X)(CHR')(Pyrrolide)(OTer) (X = NR or O; OTer = a 2,6-terphenoxide). Addition of 1-hexene or coordinating solvents such as THF do not decrease the stereospecificity of the polymerization. Cis,iso and cis,syndio dyads can be distinguished through investigation of 1H and 13C NMR spectra of the two polymers in a mixture. The polymers were hydrogenated to give isotactic and syndiotactic H-poly(NBE) and H-poly(TCD).},

  doi          = {10.1021/acs.macromol.5b00161},

  journal      = {Macromolecules},

  number       = 8,

  volume       = 48,

  place        = {United States},

  year         = {Tue Apr 07 00:00:00 EDT 2015},

  month        = {Tue Apr 07 00:00:00 EDT 2015}

}

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https://doi.org/10.1021/acscentsci.6b00200
Installing Controlled Stereo-Defects Yields Semicrystalline and Biodegradable Poly(3-Hydroxybutyrate) with High Toughness and Optical Clarity

Journal Article Quinn, Ethan C. ; Westlie, Andrea H. ; Sangroniz, Ainara ; ... - Journal of the American Chemical Society

Stereo-defects present in stereo-regular polymers often diminish thermal and mechanical properties, and hence suppressing or eliminating them is a major aspirational goal for achieving polymers with optimal or enhanced properties. Here, we accomplish the opposite by introducing controlled stereo-defects to semicrystalline biodegradable poly(3-hydroxybutyrate) (P3HB), which offers an attractive biodegradable alternative to semicrystalline isotactic polypropylene but is brittle and opaque. We enhance the specific properties and mechanical performance of P3HB by drastically toughening it and also rendering it with the desired optical clarity while maintaining its biodegradability and crystallinity. This toughening strategy of stereo-microstructural engineering without changing the chemical compositions alsomore »« less
https://doi.org/10.1021/jacs.2c12897

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Title: Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators

Abstract

Citation Formats

Recent Advances in High Oxidation State Mo and W Imido Alkylidene Chemistry journal, August 2009

High Oxidation State Multiple Metal−Carbon Bonds journal, January 2002

Ruthenium-Based Heterocyclic Carbene-Coordinated Olefin Metathesis Catalysts † journal, March 2010

Homogeneous Metathesis Polymerization by Well-Defined Group VI and Group VIII Transition-Metal Alkylidenes: Fundamentals and Applications in the Preparation of Advanced Materials journal, April 2000

Living ring-opening metathesis polymerization journal, January 2007

Bioactive and Therapeutic ROMP Polymers journal, July 2007

Recent advances in metathesis polymerisation book, January 1995

Polymer-Supported Well-Defined Metathesis Catalysts journal, November 2008

Synthesis of stereoregular ROMP polymers using molybdenum and tungsten imido alkylidene initiators journal, May 2011

Synthesis of Stereoregular Polymers through Ring-Opening Metathesis Polymerization journal, June 2014

Precise Control of Polyolefin Stereochemistry Using Single-Site Metal Catalysts journal, April 2000

Stereoselective Polymerization with Single-Site Catalysts book, November 2007

Synthesis of chiral molybdenum ROMP initiators and all-cis highly tactic poly(2,3-(R)2norbornadiene) (R = CF3 or CO2Me) journal, May 1993

Polymerization of Enantiomerically Pure 2,3-Dicarboalkoxynorbornadienes and 5,6-Disubstituted Norbornenes by Well-Characterized Molybdenum Ring-Opening Metathesis Polymerization Initiators. Direct Determination of Tacticity in Cis, Highly Tactic and Trans, Highly Tactic Polymers journal, April 1994

Ring Opening Metathesis Polymerization with Binaphtholate or Biphenolate Complexes of Molybdenum journal, January 1996

Exploring Factors That Determine Cis/Trans Structure and Tacticity in Polymers Prepared by Ring-Opening Metathesis Polymerizations with Initiators of the Type syn- and anti-Mo(NAr)(CHCMe2Ph)(OR)2. Observation of a Temperature-Dependent Cis/Trans Ratio journal, August 1995

Z-Selective Olefin Metathesis Processes Catalyzed by a Molybdenum Hexaisopropylterphenoxide Monopyrrolide Complex journal, June 2009

Five-Coordinate Rearrangements of Metallacyclobutane Intermediates during Ring-Opening Metathesis Polymerization of 2,3-Dicarboalkoxynorbornenes by Molybdenum and Tungsten Monoalkoxide Pyrrolide Initiators journal, August 2012

Z-Selective and Syndioselective Ring-Opening Metathesis Polymerization (ROMP) Initiated by Monoaryloxidepyrrolide (MAP) Catalysts journal, September 2010

Synthesis of cis,syndiotactic ROMP Polymers Containing Alternating Enantiomers journal, January 2011

Oxo vs Imido Alkylidene d 0 -Metal Species: How and Why Do They Differ in Structure, Activity, and Efficiency in Alkene Metathesis? journal, September 2012

Syndiospecific Ring-opening Metathesis Polymerization of endo-Dicyclopentadiene by Tungsten(VI) Phenylimido Catalyst journal, November 2005

Stereospecific Ring-Opening Metathesis Polymerization of Cycloolefins Using Novel Molybdenum and Tungsten Complexes Having Biphenolate Ligands. Development of Crystalline Hydrogenated Poly(endo-dicyclopentadiene) and Poly(norbornene) journal, October 2003

A New Method for Catalytic Syntheses of Block Copolymers via ROMP: Development of Stereoblock Copoly(endo-dicyclopentadiene) journal, May 2008

Stereospecific Ring-Opening Metathesis Polymerization of endo-Dicyclopentadiene by Schrock–Hoveyda Catalyst and Novel Mo- and W-based Complexes. Development of Crystalline Hydrogenated Poly(endo-dicyclopentadiene) journal, August 2003

Hydrogenated Ring-Opened Poly(endo-dicyclopentadiene)s Made via Stereoselective ROMP Catalyzed by Tungsten Complexes: Crystalline Tactic Polymers and Amorphous Atactic Polymer journal, June 2006

Syndioselective Ring-Opening Metathesis Polymerization of endo-Dicyclopentadiene with Tungsten Complexes Having Imido Ligands: Development of Crystalline Syndiotactic Hydrogenated Poly(endo-dicyclopentadiene) journal, December 2005

Iso- and Syndio-Selective ROMP of Norbornene and Tetracyclododecene: Effects of Tacticity Control on the Hydrogenated Ring-Opened Poly(cycloolefin)s journal, November 2014

The 13C NMR spectra of poly(1‐pentenylene) and poly(1,3‐cyclopentylenevinylene) journal, May 1977

Synthesis and ROMP Chemistry of Decafluoroterphenoxide Molybdenum Imido Alkylidene and Ethylene Complexes journal, May 2013

Readily Accessible and Easily Modifiable Ru-Based Catalysts for Efficient and Z -Selective Ring-Opening Metathesis Polymerization and Ring-Opening/Cross-Metathesis journal, May 2013

Determination of the Tacticity of Ring-opened Metathesis Polymers of Norbornene and Norbornadiene by13C NMR Spectroscopy of their Hydrogenated Derivatives journal, September 1996

The crystal-crystal transition in hydrogenated ring-opened polynorbornenes: Tacticity, crystal thickening, and alignment journal, September 2010

Hydrogenated Ring-Opened Polynorbornene: A Highly Crystalline Atactic Polymer journal, February 2005

Determination of the tacticities of ring-opened metathesis polymers of symmetrical 5,6-disubstituted derivatives of norbornene and norbornadiene from the 13C NMR spectra of their hydrogenated derivatives journal, July 1998

An improved method for the diimide hydrogenation of butadiene and isoprene containing polymers journal, March 1992

Stereospecific Ring-Opening Metathesis Polymerization of 3-Methyl-3-phenylcylopropene by Molybdenum Alkylidene Initiators journal, May 2008

Z-Selective Olefin Metathesis Reactions Promoted by Tungsten Oxo Alkylidene Complexes journal, December 2011

Stereospecific Ring-Opening Metathesis Polymerization of Norbornadienes Employing Tungsten Oxo Alkylidene Initiators journal, July 2014

Synthesis of molybdenum imido alkylidene complexes and some reactions involving acyclic olefins journal, May 1990

Syntheses of Tungsten tert-Butylimido and Adamantylimido Alkylidene Complexes Employing Pyridinium Chloride As the Acid journal, August 2012

Synthesis of Tungsten Oxo Alkylidene Complexes journal, October 2012

Tungsten Oxo Alkylidene Complexes as Initiators for the Stereoregular Polymerization of 2,3-Dicarbomethoxynorbornadiene journal, April 2014

Imido Alkylidene Bispyrrolyl Complexes of Tungsten journal, November 2007

Z -Selective Metathesis Homocoupling of 1,3-Dienes by Molybdenum and Tungsten Monoaryloxide Pyrrolide (MAP) Complexes journal, July 2012

Molybdenum Imido Alkylidene Metathesis Catalysts That Contain Electron-Withdrawing Biphenolates or Binaphtholates journal, April 2007

Alkylidene and Metalacyclic Complexes of Tungsten that Contain a Chiral Biphenoxide Ligand. Synthesis, Asymmetric Ring-Closing Metathesis, and Mechanistic Investigations journal, March 2003

Functional Precision Polymers via Stereo- and Regioselective Polymerization Using Group 6 Metal Alkylidene and Group 6 and 8 Metal Alkylidene N -Heterocyclic Carbene Complexes journal, August 2018

Pentamethylcyclopentadienyl Titanium(IV) Amido Pyridylene Phenylene and Pentamethylcyclopentadienyl Titanacyclopropane Amido Complexes and their Behavior in the Polymerization of Ethylene and Cyclic Olefins journal, March 2017

Addition Oligomerization of Dicyclopentadiene: Reactivity of Endo and Exo Isomers and Postmodification journal, March 2017

Tuning the phase behavior of semicrystalline hydrogenated polynorbornene via epimerization journal, December 2018

Ring-opening metathesis polymerization-induced self-assembly (ROMPISA) of a cisplatin analogue for high drug-loaded nanoparticles journal, January 2019

Recent Advances in High Oxidation State Mo and W Imido Alkylidene Chemistry
journal, August 2009

High Oxidation State Multiple Metal−Carbon Bonds
journal, January 2002

Ruthenium-Based Heterocyclic Carbene-Coordinated Olefin Metathesis Catalysts ^†
journal, March 2010

Homogeneous Metathesis Polymerization by Well-Defined Group VI and Group VIII Transition-Metal Alkylidenes: Fundamentals and Applications in the Preparation of Advanced Materials
journal, April 2000

Living ring-opening metathesis polymerization
journal, January 2007

Bioactive and Therapeutic ROMP Polymers
journal, July 2007

Recent advances in metathesis polymerisation
book, January 1995

Polymer-Supported Well-Defined Metathesis Catalysts
journal, November 2008

Synthesis of stereoregular ROMP polymers using molybdenum and tungsten imido alkylidene initiators
journal, May 2011

Synthesis of Stereoregular Polymers through Ring-Opening Metathesis Polymerization
journal, June 2014

Precise Control of Polyolefin Stereochemistry Using Single-Site Metal Catalysts
journal, April 2000

Stereoselective Polymerization with Single-Site Catalysts
book, November 2007

Synthesis of chiral molybdenum ROMP initiators and all-cis highly tactic poly(2,3-(R)2norbornadiene) (R = CF3 or CO2Me)
journal, May 1993

Polymerization of Enantiomerically Pure 2,3-Dicarboalkoxynorbornadienes and 5,6-Disubstituted Norbornenes by Well-Characterized Molybdenum Ring-Opening Metathesis Polymerization Initiators. Direct Determination of Tacticity in Cis, Highly Tactic and Trans, Highly Tactic Polymers
journal, April 1994

Ring Opening Metathesis Polymerization with Binaphtholate or Biphenolate Complexes of Molybdenum
journal, January 1996

Exploring Factors That Determine Cis/Trans Structure and Tacticity in Polymers Prepared by Ring-Opening Metathesis Polymerizations with Initiators of the Type syn- and anti-Mo(NAr)(CHCMe₂Ph)(OR)₂. Observation of a Temperature-Dependent Cis/Trans Ratio
journal, August 1995

Z-Selective Olefin Metathesis Processes Catalyzed by a Molybdenum Hexaisopropylterphenoxide Monopyrrolide Complex
journal, June 2009

Five-Coordinate Rearrangements of Metallacyclobutane Intermediates during Ring-Opening Metathesis Polymerization of 2,3-Dicarboalkoxynorbornenes by Molybdenum and Tungsten Monoalkoxide Pyrrolide Initiators
journal, August 2012

Z-Selective and Syndioselective Ring-Opening Metathesis Polymerization (ROMP) Initiated by Monoaryloxidepyrrolide (MAP) Catalysts
journal, September 2010

Synthesis of cis,syndiotactic ROMP Polymers Containing Alternating Enantiomers
journal, January 2011

Oxo vs Imido Alkylidene d ⁰ -Metal Species: How and Why Do They Differ in Structure, Activity, and Efficiency in Alkene Metathesis?
journal, September 2012

Syndiospecific Ring-opening Metathesis Polymerization of endo-Dicyclopentadiene by Tungsten(VI) Phenylimido Catalyst
journal, November 2005

Stereospecific Ring-Opening Metathesis Polymerization of Cycloolefins Using Novel Molybdenum and Tungsten Complexes Having Biphenolate Ligands. Development of Crystalline Hydrogenated Poly(endo-dicyclopentadiene) and Poly(norbornene)
journal, October 2003

A New Method for Catalytic Syntheses of Block Copolymers via ROMP: Development of Stereoblock Copoly(endo-dicyclopentadiene)
journal, May 2008

Stereospecific Ring-Opening Metathesis Polymerization of endo-Dicyclopentadiene by Schrock–Hoveyda Catalyst and Novel Mo- and W-based Complexes. Development of Crystalline Hydrogenated Poly(endo-dicyclopentadiene)
journal, August 2003

Hydrogenated Ring-Opened Poly(endo-dicyclopentadiene)s Made via Stereoselective ROMP Catalyzed by Tungsten Complexes: Crystalline Tactic Polymers and Amorphous Atactic Polymer
journal, June 2006

Syndioselective Ring-Opening Metathesis Polymerization of endo-Dicyclopentadiene with Tungsten Complexes Having Imido Ligands: Development of Crystalline Syndiotactic Hydrogenated Poly(endo-dicyclopentadiene)
journal, December 2005

Iso- and Syndio-Selective ROMP of Norbornene and Tetracyclododecene: Effects of Tacticity Control on the Hydrogenated Ring-Opened Poly(cycloolefin)s
journal, November 2014

The ¹³C NMR spectra of poly(1‐pentenylene) and poly(1,3‐cyclopentylenevinylene)
journal, May 1977

Synthesis and ROMP Chemistry of Decafluoroterphenoxide Molybdenum Imido Alkylidene and Ethylene Complexes
journal, May 2013

Readily Accessible and Easily Modifiable Ru-Based Catalysts for Efficient and Z -Selective Ring-Opening Metathesis Polymerization and Ring-Opening/Cross-Metathesis
journal, May 2013

Determination of the Tacticity of Ring-opened Metathesis Polymers of Norbornene and Norbornadiene by13C NMR Spectroscopy of their Hydrogenated Derivatives
journal, September 1996

The crystal-crystal transition in hydrogenated ring-opened polynorbornenes: Tacticity, crystal thickening, and alignment
journal, September 2010

Hydrogenated Ring-Opened Polynorbornene: A Highly Crystalline Atactic Polymer
journal, February 2005

Determination of the tacticities of ring-opened metathesis polymers of symmetrical 5,6-disubstituted derivatives of norbornene and norbornadiene from the 13C NMR spectra of their hydrogenated derivatives
journal, July 1998

An improved method for the diimide hydrogenation of butadiene and isoprene containing polymers
journal, March 1992

Stereospecific Ring-Opening Metathesis Polymerization of 3-Methyl-3-phenylcylopropene by Molybdenum Alkylidene Initiators
journal, May 2008

Z-Selective Olefin Metathesis Reactions Promoted by Tungsten Oxo Alkylidene Complexes
journal, December 2011

Stereospecific Ring-Opening Metathesis Polymerization of Norbornadienes Employing Tungsten Oxo Alkylidene Initiators
journal, July 2014

Synthesis of molybdenum imido alkylidene complexes and some reactions involving acyclic olefins
journal, May 1990

Syntheses of Tungsten tert-Butylimido and Adamantylimido Alkylidene Complexes Employing Pyridinium Chloride As the Acid
journal, August 2012

Synthesis of Tungsten Oxo Alkylidene Complexes
journal, October 2012

Tungsten Oxo Alkylidene Complexes as Initiators for the Stereoregular Polymerization of 2,3-Dicarbomethoxynorbornadiene
journal, April 2014

Imido Alkylidene Bispyrrolyl Complexes of Tungsten
journal, November 2007

Z -Selective Metathesis Homocoupling of 1,3-Dienes by Molybdenum and Tungsten Monoaryloxide Pyrrolide (MAP) Complexes
journal, July 2012

Molybdenum Imido Alkylidene Metathesis Catalysts That Contain Electron-Withdrawing Biphenolates or Binaphtholates
journal, April 2007

Alkylidene and Metalacyclic Complexes of Tungsten that Contain a Chiral Biphenoxide Ligand. Synthesis, Asymmetric Ring-Closing Metathesis, and Mechanistic Investigations
journal, March 2003

Functional Precision Polymers via Stereo- and Regioselective Polymerization Using Group 6 Metal Alkylidene and Group 6 and 8 Metal Alkylidene N -Heterocyclic Carbene Complexes
journal, August 2018

Pentamethylcyclopentadienyl Titanium(IV) Amido Pyridylene Phenylene and Pentamethylcyclopentadienyl Titanacyclopropane Amido Complexes and their Behavior in the Polymerization of Ethylene and Cyclic Olefins
journal, March 2017

Addition Oligomerization of Dicyclopentadiene: Reactivity of Endo and Exo Isomers and Postmodification
journal, March 2017

Tuning the phase behavior of semicrystalline hydrogenated polynorbornene via epimerization
journal, December 2018

Ring-opening metathesis polymerization-induced self-assembly (ROMPISA) of a cisplatin analogue for high drug-loaded nanoparticles
journal, January 2019