CaltechAUTHORS
  A Caltech Library Service

Mechanistic Insights on the Controlled Switch from Oligomerization to Polymerization of 1-Hexene Catalyzed by an NHC-Zirconium Complex

Despagnet-Ayoub, Emmanuelle and Takase, Michael K. and Henling, Lawrence M. and Labinger, Jay A. and Bercaw, John E. (2015) Mechanistic Insights on the Controlled Switch from Oligomerization to Polymerization of 1-Hexene Catalyzed by an NHC-Zirconium Complex. Organometallics, 34 (19). pp. 4707-4716. ISSN 0276-7333. https://resolver.caltech.edu/CaltechAUTHORS:20151105-082822906

[img] Crystallographic Info File (CIF) (Crystallographic data of complexes 2–4) - Supplemental Material
See Usage Policy.

10Mb
[img] PDF (GC traces of the oligomers, NMR spectra (1/B(C6F5)3/coordination of the L ligand, complexes 5 and 6, oligomers/polymers obtained), reaction profile at higher dilution, dynamic NMR study of complex 4, and crystallographic data for complexes 2–4) - Supplemental Material
See Usage Policy.

4Mb

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20151105-082822906

Abstract

The benzimidazolylidene zirconium complex 1 switches from an oligomerization (without additive) to a polymerization catalyst by addition of an L-type ligand such as trimethylphosphine, while larger phosphines or amines completely inhibit catalysis. On the basis of the regioselectivity of the oligomers/polymers obtained, the time profiles of reactions as a function of added ligand, and the molecular structures of several cationic zirconium complexes, we propose a mechanistic framework for interpreting this complex catalytic behavior.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/acs.organomet.5b00472DOIArticle
http://pubs.acs.org/doi/10.1021/acs.organomet.5b00472PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/acs.organomet.5b00472PublisherSupporting Information
ORCID:
AuthorORCID
Despagnet-Ayoub, Emmanuelle0000-0002-9013-7574
Takase, Michael K.0000-0001-8365-3645
Labinger, Jay A.0000-0002-1942-9232
Additional Information:© 2015 American Chemical Society. Received: June 5, 2015; Published: August 17, 2015. Special Issue: Gregory Hillhouse Issue. This work was supported by grants from King Fahd University of Petroleum and Minerals (Dhahran, Saudi Arabia) and the USDOE Office of Basic Energy Sciences (Grant No. DE-FG03-85ER13431). The Bruker KAPPA 30 APEXII X-ray diffractometer was purchased via an NSFCRIF:MU award to the California Institute of Technology (CHE-0639094). A tribute to Greg Hillhouse, a warm and generous human being, a creative scholar, and self-proclaimed “favorite former postdoc” of J.E.B. Author Contributions: The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
King Fahd University of Petroleum and Minerals (KFUPM)UNSPECIFIED
Department of Energy (DOE)DE-FG03-85ER13431
NSFCHE-0639094
Issue or Number:19
Record Number:CaltechAUTHORS:20151105-082822906
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20151105-082822906
Official Citation:Mechanistic Insights on the Controlled Switch from Oligomerization to Polymerization of 1-Hexene Catalyzed by an NHC-Zirconium Complex Emmanuelle Despagnet-Ayoub, Michael K. Takase, Lawrence M. Henling, Jay A. Labinger, and John E. Bercaw Organometallics 2015 34 (19), 4707-4716 DOI: 10.1021/acs.organomet.5b00472
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:61870
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:05 Nov 2015 20:04
Last Modified:09 Mar 2020 13:19

Repository Staff Only: item control page