Skip to content
DraconiticResearch
Search Sources API
203,234 studies31 sourcesUpdated just now
PreprintCC BY-NC-NDChemRxiv

Ag13Cu4 Nanocluster-Catalyzed Ambient C-F Bond Activation

  • Vivek Yadav1,2
  • Parveen Kumar1,3
  • Bokown Yoon4,5
  • Tomas Base6,7
  • Meena Nemiwal1,3
  • Uzi Landman4,5
  • THALAPPIL PRADEEP
7 affiliations
  1. 1Department of Chemistry
  2. 2Indian Institute of Technology
  3. 3MNIT Jaipur
  4. 4School of Physics
  5. 5Georgia Institute of Technology
  6. 6Institute of Inorganic Chemistry
  7. 7Czech Academy of Science
Open at sourceDOICite

Abstract

Atomically precise nanoclusters (NC) with discrete electronic states and high surface-to-atom ratios offer unique controllable active sites leading to unique catalytic transformations. Here we demonstrate that an ultrasmall (<3 nm), atomically precise Ag-Cu alloy NC, [Ag13Cu4(o1-CBT)12]3- (o1-CBT = ortho-1-carboranethiol) (Ag13Cu4), leverages these features to accomplish the extremely difficult activation and cleavage of inert C-F bond under ambient conditions. With copper atoms positioned at peripheral sites, Ag13Cu4 catalyzes room-temperature C-N cross-coupling between aryl fluorides and the pharmacologically relevant thioguanine (TG) under aerobic conditions, delivering arylated TG derivatives under operationally simple conditions. Computations revealed the evolution of atomic arrangements, superatom-delocalized electronic states of the bimetallic NC, frontier orbitals of gap-localized Cu and reactants, activation mechanism and a barrier-crossing pathway of the catalyzed reaction, culminating with the uncovering of a concerted SNAr mechanism of the reaction enabling C-F bond-activation and cleavage of benzene fluoride with a cross-coupling transformation forming a C-N bond between the phenyl group and TG molecule. This first demonstration of ambient C-F bond dissociation by an atomically precise cluster highlights a molecular materials-driven frontier in catalysis, opening futuristic pathways for synthesizing fluorinated pharmaceuticals and remediation of fluorinated environmental contaminants.

Related

  1. Pd-catalyzed, oxidant-promoted, chelation-assisted, regioselective direct ortho-nitration of 1-aryl-1H-indazoles via C–H bond activation: direct access to novel indazole-based antiproliferative agents
    Janmejaya Sen, Shivani, Pushpendra Kumar +2
    RSC advancesPeer-reviewedCC BY-NCFull textOrganic chemistryEurope PMCEurope PMCPMC
  2. Plasmonic Coupling Within Atomically Precise Nanocluster Dimers for Engineering Hot-Carrier Generation and Molecular Activation
    Khushboo Bhardwaj, Samir Kumar Nayak, Pramod K. Verma +1
    ChemRxivPreprintLicence not statedGeneral chemistryChemRxiv
  3. Visible Light‐Driven Copper‐Catalyzed Asymmetric Synthesis via Sequential C(sp 3 )─C(sp 3 ) Bond Scission
    Zhiyong Chi, Boxuan Yang, Xiaoling Cheng +2
    Angewandte Chemie International EditionPeer-reviewedLicence not statedFull text6 citedOrganic chemistryOpenAlex
  4. Optimization of Sodium-Catalyzed Si–N Bond Formation Through a Comparative Study of Group 1 Alkoxides
    Shakira A. Iyanda, Rory A. Wells, Gwyneth A. Oden +1
    ChemRxivPreprintCC BY-NC-NDFull textOrganic chemistryChemRxiv
  5. Zirconium-Mediated C–O Bond Cleavage of Alkenyl Ethers Enables Nickel-Catalyzed C(sp3)–C(sp3) and C(sp3)–C(sp2) Cross-Coupling
    Haowen Xu, Songlin Bai, Bin Yang +3
    ChemRxivPreprintCC BYFull textOrganic chemistryChemRxiv

Cite

BibTeXRIS
BibTeX
@misc{yadav2026ag13cu4,
  title = {{Ag13Cu4 Nanocluster-Catalyzed Ambient C-F Bond Activation}},
  author = {Vivek Yadav and Parveen Kumar and Bokown Yoon and Tomas Base and Meena Nemiwal and Uzi Landman and THALAPPIL PRADEEP},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15008243/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008243/v1},
  note = {CC BY-NC-ND},
}
RIS
TY  - UNPB
TI  - Ag13Cu4 Nanocluster-Catalyzed Ambient C-F Bond Activation
AU  - Vivek Yadav
AU  - Parveen Kumar
AU  - Bokown Yoon
AU  - Tomas Base
AU  - Meena Nemiwal
AU  - Uzi Landman
AU  - THALAPPIL PRADEEP
PY  - 2026
DA  - 2026/09/03
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15008243/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008243/v1
AB  - Atomically precise nanoclusters (NC) with discrete electronic states and high surface-to-atom ratios offer unique controllable active sites leading to unique catalytic transformations. Here we demonstrate that an ultrasmall (<3 nm), atomically precise Ag-Cu alloy NC, [Ag13Cu4(o1-CBT)12]3- (o1-CBT = ortho-1-carboranethiol) (Ag13Cu4), leverages these features to accomplish the extremely difficult activation and cleavage of inert C-F bond under ambient conditions. With copper atoms positioned at peripheral sites, Ag13Cu4 catalyzes room-temperature C-N cross-coupling between aryl fluorides and the pharmacologically relevant thioguanine (TG) under aerobic conditions, delivering arylated TG derivatives under operationally simple conditions. Computations revealed the evolution of atomic arrangements, superatom-delocalized electronic states of the bimetallic NC, frontier orbitals of gap-localized Cu and reactants, activation mechanism and a barrier-crossing pathway of the catalyzed reaction, culminating with the uncovering of a concerted SNAr mechanism of the reaction enabling C-F bond-activation and cleavage of benzene fluoride with a cross-coupling transformation forming a C-N bond between the phenyl group and TG molecule. This first demonstration of ambient C-F bond dissociation by an atomically precise cluster highlights a molecular materials-driven frontier in catalysis, opening futuristic pathways for synthesizing fluorinated pharmaceuticals and remediation of fluorinated environmental contaminants.
ER  -