skip to main content

DOE PAGESDOE PAGES

Title: Structural Characterization of β-Agostic Bonds in Pd-Catalyzed Polymerization

β-agostic Pd complexes are critical intermediates in catalytic reactions, such as olefin polymerization and Heck reactions. Pd β-agostic complexes, however, have eluded structural characterization, due to the fact that these highly unstable molecules are difficult to isolate. In this paper, we report the single-crystal X-ray and neutron diffraction characterization of β-agostic (α-diimine)Pd–ethyl intermediates in polymerization. Short C α–C β distances and acute Pd–C α–C β bond angles combined serve as unambiguous evidence for the β-agostic interaction. Finally, characterization of the agostic structure and the kinetic barrier for β-H elimination offer important insight into the fundamental understanding of agostic bonds and the mechanism of polymerization.
Authors:
 [1] ; ORCiD logo [1] ; ORCiD logo [2] ; ORCiD logo [1]
  1. New York Univ. (NYU), NY (United States). Dept. of Chemistry
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
Publication Date:
Grant/Contract Number:
AC05-00OR22725; CHE-1654483; DMR-0820341; DMR-1420073; OD016343
Type:
Accepted Manuscript
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 36; Journal Issue: 21; Journal ID: ISSN 0276-7333
Publisher:
American Chemical Society
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); New York Univ. (NYU), NY (United States)
Sponsoring Org:
USDOE Office of Science (SC); National Science Foundation (NSF); National Inst. of Health (NIH) (United States)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1422611

Xu, Hongwei, Hu, Chunhua Tony, Wang, Xiaoping, and Diao, Tianning. Structural Characterization of β-Agostic Bonds in Pd-Catalyzed Polymerization. United States: N. p., Web. doi:10.1021/acs.organomet.7b00666.
Xu, Hongwei, Hu, Chunhua Tony, Wang, Xiaoping, & Diao, Tianning. Structural Characterization of β-Agostic Bonds in Pd-Catalyzed Polymerization. United States. doi:10.1021/acs.organomet.7b00666.
Xu, Hongwei, Hu, Chunhua Tony, Wang, Xiaoping, and Diao, Tianning. 2017. "Structural Characterization of β-Agostic Bonds in Pd-Catalyzed Polymerization". United States. doi:10.1021/acs.organomet.7b00666. https://www.osti.gov/servlets/purl/1422611.
@article{osti_1422611,
title = {Structural Characterization of β-Agostic Bonds in Pd-Catalyzed Polymerization},
author = {Xu, Hongwei and Hu, Chunhua Tony and Wang, Xiaoping and Diao, Tianning},
abstractNote = {β-agostic Pd complexes are critical intermediates in catalytic reactions, such as olefin polymerization and Heck reactions. Pd β-agostic complexes, however, have eluded structural characterization, due to the fact that these highly unstable molecules are difficult to isolate. In this paper, we report the single-crystal X-ray and neutron diffraction characterization of β-agostic (α-diimine)Pd–ethyl intermediates in polymerization. Short Cα–Cβ distances and acute Pd–Cα–Cβ bond angles combined serve as unambiguous evidence for the β-agostic interaction. Finally, characterization of the agostic structure and the kinetic barrier for β-H elimination offer important insight into the fundamental understanding of agostic bonds and the mechanism of polymerization.},
doi = {10.1021/acs.organomet.7b00666},
journal = {Organometallics},
number = 21,
volume = 36,
place = {United States},
year = {2017},
month = {10}
}