Steering Surface Reaction Dynamics with a Self‐Assembly Strategy: Ullmann Coupling on Metal Surfaces

Zhou, Xiong; Wang, Chenguang; Zhang, Yajie; Cheng, Fang; He, Yang; Shen, Qian; Shang, Jian Ku; Shao, Xiang; Ji, Wei; Chen, Wei; Xu, Guodong; Wu, Kai

doi:10.1002/anie.201705018

Cited by 62 publications

(72 citation statements)

References 42 publications

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“…[30][31][32] In addition, additives have been used to supress acertain reaction [33,34] and preorganization by different self-assembled structures has been shownt oi nfluencet he reactivity. [35,36] Alternatively, one can run the process at different coverages [37][38][39] or temperatures [40] and use these readily varied reactionp arameters for product control.H owever, to date only few exampleso nr eactionc ontrol based on surfacec overage in two-dimensionalc hemistry have been reported. [41] Herein, we show that the surfacec overage of 6-ethynyl-2naphthoic acid (ENA 1,i ts synthesis is described in the Supporting Information) steers reaction outcomeo nt he Ag(111) substrate.…”

Section: Introductionmentioning

confidence: 99%

“…Also protective group strategies that are well established in solution‐phase chemistry have been developed . In addition, additives have been used to supress a certain reaction and preorganization by different self‐assembled structures has been shown to influence the reactivity . Alternatively, one can run the process at different coverages or temperatures and use these readily varied reaction parameters for product control.…”

Section: Introductionmentioning

confidence: 99%

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Reaction Selectivity in On‐Surface Chemistry by Surface Coverage Control—Alkyne Dimerization versus Alkyne Trimerization

Klaasen

Liu

Meng

et al. 2018

Chemistry A European J

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This work reports the influence of molecular coverage in on-surface C-C-bond formation on reaction outcome. 6-Ethynyl-2-naphthoic acid (ENA) was chosen as organic component and Ag(111) as substrate. The alkyne moiety in ENA can either react by dimerization to ENA dimers (Glaser coupling or hydroalkynylation) or cyclotrimerization to generate a benzene core as connecting moiety. Dimer formation is preferred at high surface coverage whereas trimerization is the major reaction pathway at low coverage. Mechanistic studies are provided.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Reaction Selectivity in On‐Surface Chemistry by Surface Coverage Control—Alkyne Dimerization versus Alkyne Trimerization

Klaasen

Liu

Meng

et al. 2018

Chemistry A European J

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“…showed the complete pathway of Ullmann coupling by STM and AFM. In the same year, Zhou et al. reported that the reaction pathway is influenced by whether the initially formed organometallic intermediate self‐assembled or not.…”

Section: C−x and C−h Activation Of Sp2‐carbonmentioning

confidence: 99%

On‐Surface Synthesis of One‐Dimensional Carbon‐Based Nanostructures via C−X and C−H Activation Reactions

Kang

2019

ChemPhysChem

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The past decades have witnessed the emergence of lowdimensional carbon-based nanostructures owing to their unique properties and various subsequent applications. It is of fundamental importance to explore ways to achieve atomically precise fabrication of these interesting structures. The newly developed on-surface synthesis approach provides an efficient strategy for this challenging issue, demonstrating the potential of atomically precise preparation of low-dimensional nanostructures. Up to now, the formation of various surface nanostructures, especially carbon-based ones, such as graphene nanoribbons (GNRs), kinds of organic (organometallic) chains and films, have been achieved via on-surface synthesis strategy, in which in-depth understanding of the reaction mechanism has also been explored. This review article will provide a general overview on the formation of one-dimensional carbon-based nanostructures via on-surface synthesis method. In this review, only a part of the on-surface chemical reactions (specifically, CÀ X (X=Cl, Br, I) and CÀ H activation reactions) under ultra-high vacuum conditions will be covered. CÀ X and CÀ H Activation of sp-CarbonOn-surface dehalogenative/dehydrogenative homocoupling reactions of precursors functionalized with alkynyl groups have manifested great potential for the fabrication of low-dimensional carbon-based nanostructures involving acetylenic scaffolds, such as carbyne, graphyne and graphdiyne. Sun [8] et al. reported the successful formation of one-dimensional wires with acetylenic scaffolding via on-surface CÀ Br activation of sphybridized carbon atoms. They designed and synthesized the precursor 4,4'-di(bromoethynyl)-1,1'-biphenyl (bBEBP), and then deposited it on Au(111) substrate at RT. After annealing tõ 320 K, one-dimensional chains were formed on the surface. These chains were composed of two kinds of alternating protrusions. Thus, an organometallic chain structure combined with CÀ AuÀ C was proposed (as shown in Figure 1a), with the DFT model being in good agreement with the STM image. Further annealing to~425 K leaded to Au atoms released from the organometallic chains, and consequently, CÀ C coupled molecular chains with acetylenic linkages were obtained (as shown in Figure 1b). The disappearance of dot protrusions between biphenyl groups can be observed from the STM images. Additionally, the feasibility to incorporate acetylenic scaffoldings into two-dimensional networks was also be demonstrated in this work. Liu et al. analogously synthesized graphdiyne zigzag chains and macrocycles. Statistical results showed that macrocycles were preferred to form in low coverage of organometallic intermediates. [9] These works act as a supplement to our understandings of on-surface dehalogenative homocoupling reactions, and moreover, make CÀ X activation of sp-hybridized carbon a suitable strategy to synthesize highquality nanostructures with acetylenic linkages.Glaser coupling, discovered by Glaser [10] in 1869, can also be applied to the preparation of chain structures...

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“…The self‐assembly strategy can also be utilized to change the reaction pathway via the formations of various reaction intermediates. A typical case is the Ullmann coupling of 4‐bromobiphenyl (BBP, C 6 H 5 C 6 H 4 Br) on Ag(111) . After being deposited on Ag(111) at low temperature and then warmed up to room temperature, the BBP molecules are transformed into Ag‐coordinated organometallic intermediates, C 6 H 5 C 6 H 4 AgC 6 H 4 C 6 H 5 (Ag‐COI).…”

Section: Controlling Surface Reaction Via Molecular Manipulationmentioning

confidence: 99%

Section: Controlling Surface Reaction Via Molecular Manipulationmentioning

confidence: 99%

Two‐Sidedness of Surface Reaction Mediation

et al. 2019

Self Cite

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A heterogeneous catalytic process involves many surface elementary steps that affect the overall catalytic performance in one way or another. In general, a high-performance heterogeneous catalyst should meet the main criteria: excellent catalytic activity and high selectivity toward target products. Using surface science techniques, the two-sidedness of the surface reaction mediations can be explored, from the perspectives of the surface and the molecule manipulations. The surface manipulation refers to a reaction that is mediated by composition and structure of the substrate as well as surface species, while the molecular manipulation relates to a reaction that is mediated by the reacting molecule via the precursor selection, environmental control, or external excitation. The best catalytic system should consist of the most efficient catalyst and the best suitable reacting molecule, in addition to its economic benefit and environmental amity. Recent research progress in surface reaction mediation is outlined, and its two-sidedness is governed by the Arrhenius equation. This should shed new light on the connection between basic theory and surface reaction mediation strategies. To conclude, challenges and possible opportunities are elaborated for efficient surface reaction mediations.

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Steering Surface Reaction Dynamics with a Self‐Assembly Strategy: Ullmann Coupling on Metal Surfaces

Cited by 62 publications

References 42 publications

Reaction Selectivity in On‐Surface Chemistry by Surface Coverage Control—Alkyne Dimerization versus Alkyne Trimerization

Reaction Selectivity in On‐Surface Chemistry by Surface Coverage Control—Alkyne Dimerization versus Alkyne Trimerization

On‐Surface Synthesis of One‐Dimensional Carbon‐Based Nanostructures via C−X and C−H Activation Reactions

Two‐Sidedness of Surface Reaction Mediation

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