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Steering Surface Reaction Dynamics with a Self‐Assembly Strategy: Ullmann Coupling on Metal Surfaces
Author(s) -
Zhou Xiong,
Wang Chenguang,
Zhang Yajie,
Cheng Fang,
He Yang,
Shen Qian,
Shang Jian,
Shao Xiang,
Ji Wei,
Chen Wei,
Xu Guoqin,
Wu Kai
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201705018
Subject(s) - scanning tunneling microscope , coupling (piping) , self assembly , chemical physics , coupling reaction , chemistry , reaction intermediate , surface (topology) , reaction dynamics , metal , catalysis , nanotechnology , materials science , photochemistry , molecule , organic chemistry , metallurgy , geometry , mathematics
Abstract Ullmann coupling of 4‐bromobiphenyl thermally catalyzed on Ag(111), Cu(111), and Cu(100) surfaces was scrutinized by scanning tunneling microscopy as well as theoretical calculations. Detailed experimental evidence showed that initial formation of organometallic intermediates on the surface, as self‐assembled structures or sparsely dispersed species, is determined by the subsequent reaction pathway. Specifically, the assembled organometallic intermediates at full coverage underwent a single‐barrier process to directly convert into the final coupling products, while the sparsely dispersed intermediates at low coverage went through a double‐barrier process via newly identified clover‐shaped intermediates prior to formation of the final coupling products. These findings demonstrate that a self‐assembly strategy can efficiently steer surface reaction pathways and dynamics.