Identifying Multinuclear Organometallic Intermediates in On-Surface [2+2] Cycloaddition Reactions

Zhang, Ran1; Xia, Bowen1,2; Xu, Hu2; Lin, Nian1

2019-10-04

10.1002/anie.201909278

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   影响因子和分区

1433-7851

1521-3773

We investigate the on-surface [2+2] cycloaddition reaction of 2,3,6,7,10,11-hexabromotriphenylene (HBTP) on Ag(111), Cu(111), Au(111), and Cu-dosed Au(111) surfaces using STM and DFT simulation focusing on the organometallic intermediates. The fully debrominated HBTP molecules form an organo-silver framework on Ag(111) and an organo-copper framework on Cu(111), both incorporating multinuclear metal adatom clusters. The organo-silver framework is converted into porous covalent networks via [2+2] cycloaddition above 240 degrees C. In contrast, the organo-copper framework is very stable and does not undergo [2+2] cycloaddition even at 300 degrees C. On Au(111), no organo-gold intermediate of [2+2] cycloaddition is observed. After loading Cu onto Au(111), the partially debrominated HBTP molecules bind to Cu adatom dimers to form multinuclear organo-copper complexes at 100 degrees C which undergo [2+2] cycloaddition at 140 degrees C. This study shows that the choice of surface can direct the reaction pathway.

cycloaddition reactions organometallic intermediates scanning probe microscopy surface chemistry

SCI ; EI

英语

NI期刊

其他

Hong Kong RGC[16300118]

Chemistry

Chemistry, Multidisciplinary

WOS:000491068900001

WILEY-V C H VERLAG GMBH

20194507622970

Adatoms ; Copper compounds ; Cycloaddition ; Dimers ; Molecules ; Organometallics ; Reaction intermediates ; Scanning probe microscopy ; Silver ; Surface chemistry

Precious Metals:547.1 ; Chemistry:801 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Products Generally:804 ; Organic Compounds:804.1 ; Organic Polymers:815.1.1 ; Atomic and Molecular Physics:931.3

CHEMISTRY

Web of Science

1.Hong Kong Univ Sci & Technol, Dept Phys, Hong Kong, Peoples R China
2.Southern Univ Sci & Technol, Dept Phys, Shenzhen 518055, Guangdong, Peoples R China

Zhang, Ran,Xia, Bowen,Xu, Hu,et al. Identifying Multinuclear Organometallic Intermediates in On-Surface [2+2] Cycloaddition Reactions[J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,2019,58(46):16485-16489.

Zhang, Ran,Xia, Bowen,Xu, Hu,&Lin, Nian.(2019).Identifying Multinuclear Organometallic Intermediates in On-Surface [2+2] Cycloaddition Reactions.ANGEWANDTE CHEMIE-INTERNATIONAL EDITION,58(46),16485-16489.

Zhang, Ran,et al."Identifying Multinuclear Organometallic Intermediates in On-Surface [2+2] Cycloaddition Reactions".ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 58.46(2019):16485-16489.