Reversible Dehalogenation in On‐Surface Aryl–Aryl Coupling

Stolz, Samuel; Di Giovannantonio, Marco; Urgel, José I.; Sun, Qiang; Kinikar, Amogh; Borin Barin, Gabriela; Bommert, Max; Fasel, Roman; Widmer, Roland (2020). Reversible Dehalogenation in On‐Surface Aryl–Aryl Coupling. Angewandte Chemie (International ed.), 59(33), pp. 14106-14110. Wiley-VCH 10.1002/anie.202005443

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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.

Item Type:

Journal Article (Original Article)

Division/Institute:

08 Faculty of Science > Departement of Chemistry and Biochemistry

UniBE Contributor:

Fasel, Roman

Subjects:

500 Science > 530 Physics
500 Science > 540 Chemistry

ISSN:

1433-7851

Publisher:

Wiley-VCH

Language:

English

Submitter:

Roman Fasel

Date Deposited:

03 Sep 2020 15:12

Last Modified:

03 Sep 2020 15:20

Publisher DOI:

10.1002/anie.202005443

PubMed ID:

32338418

BORIS DOI:

10.7892/boris.146329

URI:

https://boris.unibe.ch/id/eprint/146329

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