Head‐to‐Tail Oligomerization by Silylene‐Tethered Sonogashira Coupling on Ag(111). (4th June 2021)
- Record Type:
- Journal Article
- Title:
- Head‐to‐Tail Oligomerization by Silylene‐Tethered Sonogashira Coupling on Ag(111). (4th June 2021)
- Main Title:
- Head‐to‐Tail Oligomerization by Silylene‐Tethered Sonogashira Coupling on Ag(111)
- Authors:
- Sun, Kewei
Sagisaka, Keisuke
Peng, Lifen
Watanabe, Hikaru
Xu, Feng
Pawlak, Rémy
Meyer, Ernst
Okuda, Yasuhiro
Orita, Akihiro
Kawai, Shigeki - Abstract:
- Abstract: On‐surface synthesis is a powerful method for the fabrication of π‐conjugated nanomaterials. Herein, we demonstrate chemoselective Sonogashira coupling between (trimethylsilyl)ethynyl and chlorophenyl groups in silylethynyl‐ and chloro‐substituted partially fluorinated phenylene ethynylenes (SiCPFPEs) on Ag(111). The desilylative Sonogashira coupling occurred with high chemoselectivity up to 75 %, while the competing Ullmann and desilylative Glaser homocoupling reactions were suppressed. A combination of bond‐resolved scanning tunneling microscopy/atomic force microscopy (STM/AFM) and DFT calculations revealed that the oligomers were obtained by the formation of intermolecular silylene tethers (‐Me2 Si‐) through CH3 −Si bond activation at 130 °C and subsequent elimination of the tethers at an elevated temperature of 200 °C. Abstract : A coupling module composed of (trimethylsilyl)ethynyl and chlorophenyl groups selectively accelerated sluggish desilylative on‐surface Sonogashira coupling with homocoupling efficiently suppressed. Bond‐resolved scanning tunneling microscopy/atomic force microscopy (STM/AFM) with a CO‐functionalized tip enabled investigation of this coupling reaction and evaluation of its chemoselectivity (see picture).
- Is Part Of:
- Angewandte Chemie. Volume 133:Number 36(2021)
- Journal:
- Angewandte Chemie
- Issue:
- Volume 133:Number 36(2021)
- Issue Display:
- Volume 133, Issue 36 (2021)
- Year:
- 2021
- Volume:
- 133
- Issue:
- 36
- Issue Sort Value:
- 2021-0133-0036-0000
- Page Start:
- 19750
- Page End:
- 19755
- Publication Date:
- 2021-06-04
- Subjects:
- chemoselectivity -- desilylative cross-coupling -- on-surface oligomerization -- para-phenylene ethynylenes -- scanning probe microscopy
Chemistry -- Periodicals
540 - Journal URLs:
- http://onlinelibrary.wiley.com/ ↗
- DOI:
- 10.1002/ange.202102882 ↗
- Languages:
- English
- ISSNs:
- 0044-8249
- Deposit Type:
- Legaldeposit
- View Content:
- Available online (eLD content is only available in our Reading Rooms) ↗
- Physical Locations:
- British Library DSC - 0902.000000
British Library DSC - BLDSS-3PM
British Library HMNTS - ELD Digital store - Ingest File:
- 18514.xml