Structural Characterization of β-Agostic Bonds in Pd-Catalyzed Polymerization
Abstract
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.
- Authors:
-
[1];
[2];
[1]
- New York Univ. (NYU), NY (United States). Dept. of Chemistry
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (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)
- OSTI Identifier:
- 1422611
- Grant/Contract Number:
- AC05-00OR22725; CHE-1654483; DMR-0820341; DMR-1420073; OD016343
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Organometallics
- Additional Journal Information:
- Journal Volume: 36; Journal Issue: 21; Journal ID: ISSN 0276-7333
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Xu, Hongwei, Hu, Chunhua Tony, Wang, Xiaoping, and Diao, Tianning. Structural Characterization of β-Agostic Bonds in Pd-Catalyzed Polymerization. United States: N. p., 2017.
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. https://doi.org/10.1021/acs.organomet.7b00666
Xu, Hongwei, Hu, Chunhua Tony, Wang, Xiaoping, and Diao, Tianning. Mon .
"Structural Characterization of β-Agostic Bonds in Pd-Catalyzed Polymerization". United States. https://doi.org/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 = {Mon Oct 23 00:00:00 EDT 2017},
month = {Mon Oct 23 00:00:00 EDT 2017}
}
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Figures / Tables:
Scheme 1: Mechanism of ($\alpha$-diimine)Pd-Catalyzed Polymerization of Olefins
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