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Title: Identifying the missing link in catalyst transfer polymerization

Journal Article · · Nature Communications
ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Univ. of British Columbia, Vancouver, BC (Canada)
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Nickel-catalyzed catalyst transfer polycondensation (CTP) of thiophenes is an efficient strategy for the controlled synthesis of polythiophenes. However, a detailed view of its reaction mechanism has remained elusive with unresolved questions regarding the geometry and bonding of critical Ni(0) thiophene intermediates. Herein, we provide experimental and computational evidence of structurally characterized square planar η2-Ni(0)–thiophene species and their relevance to the mechanism of CTP. These results confirm the viability of C,C-η2 bound intermediates in CTP of thiophenes, providing an electronic rationale for the stability of such species, and thus that such processes can proceed as living polymerizations. We further show that C,S-κ2 species may also be relevant in nickel-catalyzed CTP of thiophenes, providing new avenues for exploitation and optimization.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER); Natural Sciences and Engineering Research Council of Canada (NSERC); National Institutes of Health (NIH), National Institute of General Medical Sciences (NIGMS)
Grant/Contract Number:
AC02-76SF00515; P41GM103393
OSTI ID:
1624115
Journal Information:
Nature Communications, Vol. 9, Issue 1; ISSN 2041-1723
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 19 works
Citation information provided by
Web of Science

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Cited By (4)

Aldehydes and ketones influence reactivity and selectivity in nickel-catalysed Suzuki–Miyaura reactions journal January 2020
A robust nickel catalyst with an unsymmetrical propyl-bridged diphosphine ligand for catalyst-transfer polymerization journal September 2019
The Importance of Ligand‐Induced Backdonation in the Stabilization of Square Planar d 10 Nickel π‐Complexes journal March 2019
Catalyst-transfer polymerization of arylamines by the Buchwald–Hartwig cross-coupling journal January 2019

Linked Research (2)

Figures / Tables (8)

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