2024-03-28T23:22:23Z
https://tsukuba.repo.nii.ac.jp/oai
oai:tsukuba.repo.nii.ac.jp:00054893
2023-02-02T23:46:34Z
117:1221
117:500
3:62:5296:8005
Mechanistic Study of Pd/Ag Dual-Catalyzed Cross-Dehydrogenative Coupling of Perfluoroarenes with Thiophenes
桑原, 純平
クワバラ, ジュンペイ
KUWABARA, Junpei
神原, 貴樹
カンバラ, タカキ
KANBARA, Takaki
Shimoyama, Yuto
open access
© 2020 American Chemical Society
This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Catalysis, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acscatal.9b05326.
The mechanism of the Pd/Ag dual-catalyzed cross-dehydrogenative coupling (CDC) between perfluoroarenes and thiophenes was clarified. The exact role of the catalytic resting state of the homo-biaryl-Pd(II) complex, which was previously overlooked in Pd/Ag dual-catalyzed CDC, was carefully investigated. Detailed experimental studies indicated that a homo-biaryl-Pd(II) complex occurred in the catalytic off-cycle as a resting state and prevented the homocoupling of perfluoroarenes. In addition, these studies indicated that the C–H bond activation steps of perfluoroarenes and thiophenes proceeded by different mechanisms. While the C–H bond of perfluoroarenes was immediately activated by Ag(I) salts, the C–H bond of thiophenes was activated by the Pd(II) catalyst. Kinetic studies revealed that the Pd(II)–C–H activation of thiophenes is most likely the rate-determining step.
American Chemical Society
2020-03
eng
journal article
AM
http://hdl.handle.net/2241/00160299
https://tsukuba.repo.nii.ac.jp/records/54893
https://doi.org/10.1021/acscatal.9b05326
2155-5435
AA12599706
ACS Catalysis
10
5
3390
3397
https://tsukuba.repo.nii.ac.jp/record/54893/files/ACSCatal_10-5.pdf
application/pdf
727.7 kB
2021-04-01