Journal article
Reversible Dehalogenation in On-Surface Aryl-Aryl Coupling.
- Stolz S Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600, Dübendorf, Switzerland.
- Di Giovannantonio M Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600, Dübendorf, Switzerland.
- Urgel JI Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600, Dübendorf, Switzerland.
- Sun Q Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600, Dübendorf, Switzerland.
- Kinikar A Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600, Dübendorf, Switzerland.
- Borin Barin G Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600, Dübendorf, Switzerland.
- Bommert M Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600, Dübendorf, Switzerland.
- Fasel R Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600, Dübendorf, Switzerland.
- Widmer R Empa, Swiss Federal Laboratories for Materials Science and Technology, nanotech@surfaces Laboratory, 8600, Dübendorf, Switzerland.
- 2020-04-28
Published in:
- Angewandte Chemie (International ed. in English). - 2020
English
In the emerging field of on-surface synthesis, dehalogenative aryl-aryl coupling is unarguably the most prominent tool for the fabrication of covalently bonded carbon-based nanomaterials. Despite its importance, the reaction kinetics are still poorly understood. Here we present a comprehensive temperature-programmed x-ray photoelectron spectroscopy investigation of reaction kinetics and energetics in the prototypical on-surface dehalogenative polymerization of 4,4''-dibromo-p-terphenyl into poly(para-phenylene) on two coinage metal surfaces, Cu(111) and Au(111). We find clear evidence for reversible dehalogenation on Au(111), which is inhibited on Cu(111) owing to the formation of organometallic intermediates. The incorporation of reversible dehalogenation in the reaction rate equations leads to excellent agreement with experimental data and allows extracting the relevant energy barriers. Our findings deepen the mechanistic understanding and call for its reassessment for surface-confined aryl-aryl coupling on the most frequently used metal substrates.
- Language
-
- English
- Open access status
- closed
- Identifiers
-
- DOI 10.1002/anie.202005443
- PMID 32338418
- Persistent URL
- https://sonar.ch/global/documents/39648
Statistics
Document views: 32
File downloads: