Precise Monoselective Aromatic C-H Bond Activation by Chemisorption of Meta-Aryne on a Metal Surface

Journal of the American Chemical Society
Qitang FanJ Michael Gottfried

Abstract

Aromatic C-H bond activation has attracted much attention due to its versatile applications in the synthesis of aryl-containing chemicals. The major challenge lies in the minimization of the activation barrier and maximization of the regioselectivity. Here, we report the highly selective activation of the central aromatic C-H bond in meta-aryne species anchored to a copper surface, which catalyzes the C-H bond dissociation. Two prototype molecules, i.e., 4',6'-dibromo- meta-terphenyl and 3',5'-dibromo- ortho-terphenyl, have been employed to perform C-C coupling reactions on Cu(111). The chemical structures of the resulting products have been clarified by a combination of scanning tunneling microscopy and noncontact atomic force microscopy. Both methods demonstrate a remarkable weakening of the targeted C-H bond. Density functional theory calculations reveal that this efficient C-H activation stems from the extraordinary chemisorption of the meta-aryne on the Cu(111) surface, resulting in the close proximity of the targeted C-H group to the Cu(111) surface and the absence of planarity of the phenyl ring. These effects lead to a lowering of the C-H dissociation barrier from 1.80 to 1.12 eV, in agreement with the experimental data.

References

Dec 15, 1994·Physical Review. B, Condensed Matter·P E Blöchl
Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
Jun 24, 2006·Chemistry : a European Journal·Carmen RomeroEnrique Guitián
Aug 16, 2008·Nature·Gonzalo OteroJosé A Martín-Gago
Jul 24, 2010·Nature·Jinming CaiRoman Fasel
Nov 26, 2010·Chemical Society Reviews·Tanya C Boorman, Igor Larrosa
Mar 11, 2011·Chemical Society Reviews·Lindsay McMurrayMatthew J Gaunt
Mar 11, 2011·Chemical Society Reviews·Huw M L DaviesJin-Quan Yu
Jul 19, 2011·Journal of the American Chemical Society·Weihua WangNian Lin
Dec 15, 2011·Accounts of Chemical Research·Keary M EngleJin-Quan Yu
Jun 28, 2012·Chemistry : a European Journal·David Y-K Chen, So Won Youn
Sep 29, 2012·Science·Liam T BallChristopher A Russell
Mar 21, 2013·Angewandte Chemie·Qitang FanJ Michael Gottfried
Jul 2, 2014·Chemical Society Reviews·Fengzhi Zhang, David R Spring
Aug 8, 2014·Nature·Juan Ramon Sanchez-ValenciaRoman Fasel
Aug 27, 2014·Chemical Communications : Chem Comm·Qiang SunWei Xu
Sep 10, 2014·Nature Nanotechnology·Jinming CaiRoman Fasel
Dec 20, 2014·Organic & Biomolecular Chemistry·Jiong Yang
Jan 13, 2015·Chemical Communications : Chem Comm·Qiang SunWei Xu
Jul 25, 2015·Chemical Communications : Chem Comm·Atena Rastgoo LahroodMarkus Lackinger
Jan 16, 2016·The Journal of Organic Chemistry·Huw M L Davies, Daniel Morton
Feb 9, 2016·Journal of the American Chemical Society·Qing LiLifeng Chi
Feb 13, 2016·Advanced Materials·Leopold TalirzRoman Fasel
Mar 25, 2016·Nature·Pascal RuffieuxRoman Fasel
Apr 10, 2016·Journal of the American Chemical Society·Nemanja KocićShi-Xia Liu
Aug 23, 2016·ACS Nano·Dimas G de OteyzaDiego Peña
Sep 17, 2016·Angewandte Chemie·Peter H JacobseIngmar Swart
Feb 14, 2017·Nature Nanotechnology·Niko PavličekLeo Gross
May 31, 2017·Chemical Communications : Chem Comm·Cheng-Xin WangPei-Nian Liu
Nov 8, 2017·Journal of the American Chemical Society·Carlos Sánchez-SánchezVincent Meunier

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Citations

Oct 15, 2019·Angewandte Chemie·Mykola TelychkoJiong Lu
Oct 17, 2018·Chemistry : a European Journal·Manuel Vilas-VarelaDiego Peña
Aug 18, 2018·Nature Communications·Qigang ZhongAndré Schirmeisen
Apr 3, 2020·Chemical Communications : Chem Comm·Lin FengJunfa Zhu
Jun 13, 2019·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Qitang Fan, J Michael Gottfried
Apr 19, 2020·Nature Nanotechnology·Angela B GrommetRafal Klajn
Jul 31, 2020·Chemistry : a European Journal·Jindong RenHarald Fuchs
Apr 28, 2021·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Jacob D TeeterAxel Enders
Aug 17, 2021·Journal of the American Chemical Society·Deng-Yuan LiPei-Nian Liu
Sep 19, 2019·Journal of the American Chemical Society·Iago PozoDolores Pérez
Jul 8, 2020·The Journal of Physical Chemistry Letters·Tao WangJunfa Zhu
Sep 22, 2018·Journal of the American Chemical Society·Tao WangJunfa Zhu
Dec 17, 2019·Journal of the American Chemical Society·Qitang FanJ Michael Gottfried
Dec 11, 2021·Nanoscale Horizons : the Home for Rapid Reports of Exceptional Significance in Nanoscience and Nanotechnolgy·Lukas GrossmannMarkus Lackinger

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