skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Metathesis catalysts and methods thereof

Abstract

The present application provides, among other things, novel compounds for metathesis reactions, and methods for preparing and using provided compounds. In some embodiments, the present invention provides compounds having the structure of formula I or II. In some embodiments, the present invention provides methods for preparing a compound of formula I or II. In some embodiments, the present invention provides methods for using a provided compound. In some embodiments, a provided compound is useful for stereoselective ring-opening metathesis polymerization. In some embodiments, a provided metathesis method provides cis and/or isotactic polymers.

Inventors:
;
Publication Date:
Research Org.:
Massachusetts Institute of Technology, Cambridge, MA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1248013
Patent Number(s):
9,315,604
Application Number:
14/248,712
Assignee:
Massachusetts Institute of Technology (Cambridge, MA)
DOE Contract Number:  
FG02-86ER13564
Resource Type:
Patent
Resource Relation:
Patent File Date: 2014 Apr 09
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Schrock, Richard Royce, and Yuan, Jian. Metathesis catalysts and methods thereof. United States: N. p., 2016. Web.
Schrock, Richard Royce, & Yuan, Jian. Metathesis catalysts and methods thereof. United States.
Schrock, Richard Royce, and Yuan, Jian. Tue . "Metathesis catalysts and methods thereof". United States. https://www.osti.gov/servlets/purl/1248013.
@article{osti_1248013,
title = {Metathesis catalysts and methods thereof},
author = {Schrock, Richard Royce and Yuan, Jian},
abstractNote = {The present application provides, among other things, novel compounds for metathesis reactions, and methods for preparing and using provided compounds. In some embodiments, the present invention provides compounds having the structure of formula I or II. In some embodiments, the present invention provides methods for preparing a compound of formula I or II. In some embodiments, the present invention provides methods for using a provided compound. In some embodiments, a provided compound is useful for stereoselective ring-opening metathesis polymerization. In some embodiments, a provided metathesis method provides cis and/or isotactic polymers.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {2016},
month = {4}
}

Patent:

Save / Share:

Works referenced in this record:

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

  • Yuan, Jian; Schrock, Richard R.; Gerber, Laura C. H.
  • Organometallics, Vol. 32, Issue 10, p. 2983-2992
  • DOI: 10.1021/om400199u

Pentafluorophenylimido Alkylidene Complexes of Molybdenum and Tungsten
journal, June 2012

  • Yuan, Jian; Schrock, Richard R.; Müller, Peter
  • Organometallics, Vol. 31, Issue 13
  • DOI: 10.1021/om300408n

Room-Temperature Z -Selective Homocoupling of α-Olefins by Tungsten Catalysts
journal, April 2011

  • Marinescu, Smaranda C.; Schrock, Richard R.; Müller, Peter
  • Organometallics, Vol. 30, Issue 7
  • DOI: 10.1021/om200150c

Preparation of Tungsten-Based Olefin Metathesis Catalysts Supported on Alumina
journal, July 2011

  • Yuan, Jian; Townsend, Erik M.; Schrock, Richard R.
  • Advanced Synthesis & Catalysis, Vol. 353, Issue 11-12, p. 1985-1992
  • DOI: 10.1002/adsc.201100200

Evaluation of Molybdenum and Tungsten Metathesis Catalysts for Homogeneous Tandem Alkane Metathesis
journal, January 2009

  • Bailey, Brad C.; Schrock, Richard R.; Kundu, Sabuj
  • Organometallics, Vol. 28, Issue 1
  • DOI: 10.1021/om800877q

Chemical transformations of cis -W(CO) 4 (C 5 H 5 N) 2 in the ring-opening metathesis polymerization of norbornene
journal, April 2004

  • Bencze, L.; Bíró, N.; Szabó-Ravasz, B.
  • Canadian Journal of Chemistry, Vol. 82, Issue 4
  • DOI: 10.1139/v04-007

Vinylcarbene Complexes of Titanocene
journal, May 1989

  • Binger, Paul; Müller, Patrik; Benn, Reinhard
  • Angewandte Chemie International Edition in English, Vol. 28, Issue 5, p. 610-611
  • DOI: 10.1002/anie.198906101

X-ray crystallographic studies on octahedral oxo alkylidene complexes of tungsten(VI): W(O)(CHCMe3)(PMe3)2Cl2 and W(O)(CHCMe3)(PEt3)2Cl2
journal, January 1981

  • Churchill, Melvyn Rowen; Rheingold, Arnold L.; Youngs, Wiley J.
  • Journal of Organometallic Chemistry, Vol. 204, Issue 2
  • DOI: 10.1016/S0022-328X(00)84595-7

(2-Methoxy-1,3-phenylene)diboronic acid
journal, January 2008

  • Dąbrowski, Marek; Luliński, Sergiusz; Serwatowski, Janusz
  • Acta Crystallographica Section E Structure Reports Online, Vol. 64, Issue 2
  • DOI: 10.1107/S160053680800010X

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

  • Flook, Margaret M.; Jiang, Annie J.; Schrock, Richard R.
  • Journal of the American Chemical Society, Vol. 131, Issue 23, p. 7962-7963
  • DOI: 10.1021/ja902738u

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

  • Flook, Margaret M.; Gerber, Laura C. H.; Debelouchina, Galia T.
  • Macromolecules, Vol. 43, Issue 18, p. 7515-7522
  • DOI: 10.1021/ma101375v

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

  • Flook, Margaret M.; Ng, Victor W. L.; Schrock, Richard R.
  • Journal of the American Chemical Society, Vol. 133, Issue 6, p. 1784-1786
  • DOI: 10.1021/ja110949f

Simple, high yield syntheses of molybdenum(VI) bis(imido) complexes of the type Mo(NR)2Cl2(1,2-dimethoxyethane)
journal, May 1992

  • Fox, Harold H.; Yap, Kimo B.; Robbins, Jennifer
  • Inorganic Chemistry, Vol. 31, Issue 11
  • DOI: 10.1021/ic00037a056

Catalytic Alkane Metathesis by Tandem Alkane Dehydrogenation-Olefin Metathesis
journal, April 2006

  • Goldman, Alan S.; Roy, Amy H.; Huang, Zheng
  • Science, Vol. 312, Issue 5771, p. 257-261
  • DOI: 10.1126/science.1123787

Olefin-Metathesis Catalysts for the Preparation of Molecules and Materials (Nobel Lecture)
journal, June 2006

  • Grubbs, Robert H.
  • Angewandte Chemie International Edition, Vol. 45, Issue 23, p. 3760-3765
  • DOI: 10.1002/anie.200600680

Thermodynamics, Kinetics, and Mechanism of (silox) 3 M(olefin) to (silox) 3 M(alkylidene) Rearrangements (silox = t Bu 3 SiO; M = Nb, Ta)
journal, April 2005

  • Hirsekorn, Kurt F.; Veige, Adam S.; Marshak, Michael P.
  • Journal of the American Chemical Society, Vol. 127, Issue 13
  • DOI: 10.1021/ja046180k

Dipyrrolyl Precursors to Bisalkoxide Molybdenum Olefin Metathesis Catalysts
journal, December 2006

  • Hock, A. S.; Schrock, Richard R.; Hoveyda, Amir H.
  • Journal of the American Chemical Society, Vol. 128, Issue 50
  • DOI: 10.1021/ja0665904

Highly Z - and Enantioselective Ring-Opening/Cross-Metathesis Reactions Catalyzed by Stereogenic-at-Mo Adamantylimido Complexes
journal, March 2009

  • Ibrahem, Ismail; Yu, Miao; Schrock, Richard R.
  • Journal of the American Chemical Society, Vol. 131, Issue 11
  • DOI: 10.1021/ja900097n

Fundamental Studies of Tungsten Alkylidene Imido Monoalkoxidepyrrolide Complexes
journal, June 2009

  • Jiang, Annie J.; Simpson, Jeffrey H.; Müller, Peter
  • Journal of the American Chemical Society, Vol. 131, Issue 22
  • DOI: 10.1021/ja9012694

Highly Z -Selective Metathesis Homocoupling of Terminal Olefins
journal, November 2009

  • Jiang, Annie J.; Zhao, Yu; Schrock, Richard R.
  • Journal of the American Chemical Society, Vol. 131, Issue 46
  • DOI: 10.1021/ja908098t

Cationic Molybdenum Imido Alkylidene Complexes
journal, September 2008

  • Jiang, Annie J.; Schrock, Richard R.; Müller, Peter
  • Organometallics, Vol. 27, Issue 17
  • DOI: 10.1021/om800209b

Synthesis of tungsten vinyl alkylidene complexes via the reactions of WCl2(NAr)(PX3)3 (X = R, OMe) precursors with 3,3-disubstituted cyclopropenes
journal, September 1993

  • Johnson, Lynda K.; Grubbs, Robert H.; Ziller, Joseph W.
  • Journal of the American Chemical Society, Vol. 115, Issue 18, p. 8130-8145
  • DOI: 10.1021/ja00071a026

Inversion of Configuration at the Metal in Diastereomeric Imido Alkylidene Monoaryloxide Monopyrrolide Complexes of Molybdenum
journal, January 2009

  • Marinescu, Smaranda C.; Schrock, Richard R.; Li, Bo
  • Journal of the American Chemical Society, Vol. 131, Issue 1
  • DOI: 10.1021/ja808308e

Syntheses of Variations of Stereogenic-at-Metal Imido Alkylidene Complexes of Molybdenum
journal, August 2012

  • Marinescu, Smaranda C.; Ng, Victor W. L.; Lichtscheidl, Alejandro G.
  • Organometallics, Vol. 31, Issue 17
  • DOI: 10.1021/om300585s

Syntheses and Structures of Molybdenum Imido Alkylidene Pyrrolide and Indolide Complexes
journal, December 2008

  • Marinescu, Smaranda C.; Singh, Rojendra; Hock, Adam S.
  • Organometallics, Vol. 27, Issue 24
  • DOI: 10.1021/om800816q

Simple Molybdenum(IV) Olefin Complexes of the Type Mo(NR)(X)(Y)(olefin)
journal, December 2010

  • Marinescu, Smaranda C.; King, Annie J.; Schrock, Richard R.
  • Organometallics, Vol. 29, Issue 24
  • DOI: 10.1021/om101003v

Catalytic Z-selective olefin cross-metathesis for natural product synthesis
journal, March 2011

  • Meek, Simon J.; O’Brien, Robert V.; Llaveria, Josep
  • Nature, Vol. 471, Issue 7339
  • DOI: 10.1038/nature09957

Practical suggestions for better crystal structures
journal, January 2009


Ring-opening metathesis polymerization (ROMP) of norbornene by a Group VIII carbene complex in protic media
journal, May 1992

  • Nguyen, SonBinh T.; Johnson, Lynda K.; Grubbs, Robert H.
  • Journal of the American Chemical Society, Vol. 114, Issue 10, p. 3974-3975
  • DOI: 10.1021/ja00036a053

Preparation of Well-Defined, Metathetically Active Oxo Alkylidene Complexes of Tungsten
journal, January 1996

  • O'Donoghue, M. B.; Schrock, R. R.; LaPointe, A. M.
  • Organometallics, Vol. 15, Issue 5
  • DOI: 10.1021/om950857i

Synthesis of Tungsten Oxo Alkylidene Complexes
journal, October 2012

  • Peryshkov, Dmitry V.; Schrock, Richard R.
  • Organometallics, Vol. 31, Issue 20, p. 7278-7286
  • DOI: 10.1021/om3008579

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

  • Peryshkov, Dmitry V.; Schrock, Richard R.; Takase, Michael K.
  • Journal of the American Chemical Society, Vol. 133, Issue 51, p. 20754-20757
  • DOI: 10.1021/ja210349m

Olefin metathesis - a mechanistic study of high-valent Group VI catalysts
journal, January 1982

  • Rappe, Anthony K.; Goddard, William A.
  • Journal of the American Chemical Society, Vol. 104, Issue 2
  • DOI: 10.1021/ja00366a013

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

  • Schrock, Richard R.
  • Dalton Transactions, Vol. 40, Issue 29, p. 7484-7495
  • DOI: 10.1039/C1DT10215J

Catalytic Homologation of Vinyltributylstannane to Allyltributylstannane by Mo(IV) Complexes in the Presence of Ethylene
journal, February 2004

  • Schrock, Richard R.; Duval-Lungulescu, M.; Tsang, W. C. Peter
  • Journal of the American Chemical Society, Vol. 126, Issue 7
  • DOI: 10.1021/ja039173p

Olefin Metathesis Reactions Initiated by d 2 Molybdenum or Tungsten Complexes
journal, October 2005

  • Schrock, Richard R.; Lopez, Lourdes Pia H.; Hafer, Jillian
  • Organometallics, Vol. 24, Issue 22
  • DOI: 10.1021/om050583r

Recent advances in olefin metathesis by molybdenum and tungsten imido alkylidene complexes
journal, April 2004


Multiple Metal–Carbon Bonds for Catalytic Metathesis Reactions (Nobel Lecture)
journal, June 2006

  • Schrock, Richard R.
  • Angewandte Chemie International Edition, Vol. 45, Issue 23, p. 3748-3759
  • DOI: 10.1002/anie.200600085

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


Phase annealing in SHELX-90: direct methods for larger structures
journal, June 1990

  • Sheldrick, G. M.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 46, Issue 6, p. 467-473
  • DOI: 10.1107/S0108767390000277

A short history of SHELX
journal, December 2007

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
  • DOI: 10.1107/S0108767307043930

Preparation and olefin-metathesis activity of cyclopentylidene-oxo initiator sites on a molybdenum carbide surface
journal, December 2006

  • Siaj, Mohamed; Temprano, Israel; Dubuc, Nathalie
  • Journal of Organometallic Chemistry, Vol. 691, Issue 24-25, p. 5497-5504
  • DOI: 10.1016/j.jorganchem.2006.09.033

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

  • Townsend, Erik M.; Schrock, Richard R.; Hoveyda, Amir H.
  • Journal of the American Chemical Society, Vol. 134, Issue 28
  • DOI: 10.1021/ja303220j

Molybdenum-Based Complexes with Two Aryloxides and a Pentafluoroimido Ligand: Catalysts for Efficient Z-Selective Synthesis of a Macrocyclic Trisubstituted Alkene by Ring-Closing Metathesis
journal, January 2013

  • Wang, Chenbo; Haeffner, Fredrik; Schrock, Richard R.
  • Angewandte Chemie International Edition, Vol. 52, Issue 7, p. 1939-1943
  • DOI: 10.1002/anie.201209180