Skip to content Skip to navigation
University of Warwick
  • Study
  • |
  • Research
  • |
  • Business
  • |
  • Alumni
  • |
  • News
  • |
  • About

University of Warwick
Publications service & WRAP

Highlight your research

  • WRAP
    • Home
    • Search WRAP
    • Browse by Warwick Author
    • Browse WRAP by Year
    • Browse WRAP by Subject
    • Browse WRAP by Department
    • Browse WRAP by Funder
    • Browse Theses by Department
  • Publications Service
    • Home
    • Search Publications Service
    • Browse by Warwick Author
    • Browse Publications service by Year
    • Browse Publications service by Subject
    • Browse Publications service by Department
    • Browse Publications service by Funder
  • Help & Advice
University of Warwick

The Library

  • Login
  • Admin

Mechanism of the bis(imino)pyridine-iron-catalyzed hydromagnesiation of styrene derivatives

Tools
- Tools
+ Tools

Neate, Peter G. N., Greenhalgh, Mark D., Brennessel, William W., Thomas, Stephen P. and Neidig, Michael L. (2019) Mechanism of the bis(imino)pyridine-iron-catalyzed hydromagnesiation of styrene derivatives. Journal of the American Chemical Society, 141 (25). pp. 10099-10108. doi:10.1021/jacs.9b04869

Research output not available from this repository, contact author.
Official URL: https://pubs.acs.org/doi/abs/10.1021/jacs.9b04869

Request Changes to record.

Abstract

Iron-catalyzed hydromagnesiation of styrene derivatives offers a rapid and efficient method to generate benzylic Grignard reagents, which can be applied in a range of transformations to provide products of formal hydrofunctionalization. While iron-catalyzed methodologies exist for the hydromagnesiation of terminal alkenes, internal alkynes, and styrene derivatives, the underlying mechanisms of catalysis remain largely undefined. To address this issue and determine the divergent reactivity from established cross-coupling and hydrofunctionalization reactions, a detailed study of the bis(imino)pyridine iron-catalyzed hydromagnesiation of styrene derivatives is reported. Using a combination of kinetic analysis, deuterium labeling, and reactivity studies as well as in situ Fe Mössbauer spectroscopy, key mechanistic features and species were established. A formally iron(0) ate complex [ BIPFe(Et)(CH═CH)] was identified as the principle resting state of the catalyst. Dissociation of ethene forms the catalytically active species which can reversibly coordinate the styrene derivative and mediate a direct and reversible β-hydride transfer, negating the necessity of a discrete iron hydride intermediate. Finally, displacement of the tridentate bis(imino)pyridine ligand over the course of the reaction results in the formation of a tris-styrene-coordinated iron(0) complex, which is also a competent catalyst for hydromagnesiation.

Item Type: Journal Article
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Science > Chemistry
Journal or Publication Title: Journal of the American Chemical Society
Publisher: ACS Publications
ISSN: 1520-5126
Official Date: 26 June 2019
Dates:
DateEvent
26 June 2019Published
31 May 2019Available
6 May 2019Accepted
Volume: 141
Number: 25
Page Range: pp. 10099-10108
DOI: 10.1021/jacs.9b04869
Status: Peer Reviewed
Publication Status: Published
Access rights to Published version: Restricted or Subscription Access
Funder: National Institutes of Health, NSF
Grant number: R01 GM111480/GM/NIGMS NIH HHS/United States; NSF CHE-1725028

Request changes or add full text files to a record

Repository staff actions (login required)

View Item View Item
twitter

Email us: wrap@warwick.ac.uk
Contact Details
About Us