---
OA_place: publisher
OA_type: hybrid
PlanS_conform: '1'
_id: '19599'
abstract:
- lang: eng
  text: Advances in nickel catalysis have significantly broadened the synthetic chemists’
    toolbox, particularly through methodologies leveraging paramagnetic nickel species
    via photoredox catalysis or electrochemistry. Key to these reactions is the oxidation
    state modulation of nickel via single-electron transfer events. Recent mechanistic
    studies indicate that C(sp2)–heteroatom bond formations proceed through NiI/NiIII
    cycles. Related C(sp2)–C(sp3) cross-couplings operate via the photocatalytic generation
    of C-centered radicals and a catalytic cycle that involves Ni0, NiI, and NiIII
    species. Here, we show that light-mediated nickel-catalyzed C(sp2)–C(sp3) bond
    formations can be carried out without using exogenous photoredox catalysts but
    with a photoactive ligand. In a pursuit of expanding the scope of C(sp2)–heteroatom
    couplings using donor–acceptor ligands, we identified a photoactive nickel complex
    capable of catalyzing cross-couplings between aryl halides and benzyltrifluoroborate
    salts. Mechanistic investigations provide evidence that transmetalation between
    a photochemically generated NiI species and the organoboron compound is the key
    catalytic step in a NiI/NiIII catalytic cycle under these conditions.
acknowledged_ssus:
- _id: LifeSc
- _id: NMR
acknowledgement: This research was supported by the Scientific Service Units (SSU)
  of ISTA through resources provided by the Lab Support Facility (LSF), Mass Spec
  Facility, and NMR Facility. We gratefully acknowledge the Institute of Science and
  Technology Austria (ISTA) and the Max-Planck Society for their generous financial
  support. R.M.v.d.V. and B.P. thank the Deutsche Forschungsgemeinschaft (DFG, German
  Research Foundation) under Germany’s Excellence Strategy – EXC 2008 – 390540038
  – UniSysCat for funding. B.P. thanks the DFG (PI 1635/2-19), the Boehringer Ingelheim
  Foundation (Plus 3 Perspectives Programme), and the FWF (Austrian Science Fund;
  PAT 1250924) for financial support. J.H.B. acknowledges the Robert C. and Carolyn
  J. Springborn Endowment for Student Support Program at the University of Illinois
  Urbana–Champaign. R.F.W. was supported by a fellowship from the Deutscher Akademischer
  Austauschdienst (DAAD). We thank Dr. John J. Molloy (MPICI) for scientific discussions.
article_processing_charge: Yes (via OA deal)
article_type: original
author:
- first_name: Lucia
  full_name: Anghileri, Lucia
  id: 7b65e46e-1f51-11f0-8ea0-faa153157f5e
  last_name: Anghileri
- first_name: Haralds
  full_name: Baunis, Haralds
  id: 2eea55ec-e8ec-11ed-86cb-d9c76787acfe
  last_name: Baunis
- first_name: Aleksander
  full_name: Bena, Aleksander
  id: 4197c39e-e8ec-11ed-86cb-afed934cd664
  last_name: Bena
- first_name: Christos
  full_name: Giannoudis, Christos
  id: 1bd506c6-e8ec-11ed-86cb-d495f63f2dcd
  last_name: Giannoudis
- first_name: John H.
  full_name: Burke, John H.
  last_name: Burke
- first_name: Susanne
  full_name: Reischauer, Susanne
  last_name: Reischauer
- first_name: Christoph
  full_name: Merschjann, Christoph
  last_name: Merschjann
- first_name: Rachel F.
  full_name: Wallick, Rachel F.
  last_name: Wallick
- first_name: Tarek
  full_name: Al Said, Tarek
  last_name: Al Said
- first_name: Callum E
  full_name: Adams, Callum E
  id: 126d6d0f-fdc1-11ee-bb4a-9f462709fa9d
  last_name: Adams
- first_name: Gianluca
  full_name: Simionato, Gianluca
  last_name: Simionato
- first_name: Sergey
  full_name: Kovalenko, Sergey
  last_name: Kovalenko
- first_name: Luca
  full_name: Dell’Amico, Luca
  last_name: Dell’Amico
- first_name: Renske M.
  full_name: Van Der Veen, Renske M.
  last_name: Van Der Veen
- first_name: Bartholomäus
  full_name: Pieber, Bartholomäus
  id: 93e5e5b2-0da6-11ed-8a41-af589a024726
  last_name: Pieber
  orcid: 0000-0001-8689-388X
citation:
  ama: Anghileri L, Baunis H, Bena A, et al. Evidence for a unifying NiI/NiIII mechanism
    in light-mediated cross-coupling catalysis. <i>Journal of the American Chemical
    Society</i>. 2025;147(16):13169–13179. doi:<a href="https://doi.org/10.1021/jacs.4c16050">10.1021/jacs.4c16050</a>
  apa: Anghileri, L., Baunis, H., Bena, A., Giannoudis, C., Burke, J. H., Reischauer,
    S., … Pieber, B. (2025). Evidence for a unifying NiI/NiIII mechanism in light-mediated
    cross-coupling catalysis. <i>Journal of the American Chemical Society</i>. American
    Chemical Society. <a href="https://doi.org/10.1021/jacs.4c16050">https://doi.org/10.1021/jacs.4c16050</a>
  chicago: Anghileri, Lucia, Haralds Baunis, Aleksander Bena, Christos Giannoudis,
    John H. Burke, Susanne Reischauer, Christoph Merschjann, et al. “Evidence for
    a Unifying NiI/NiIII Mechanism in Light-Mediated Cross-Coupling Catalysis.” <i>Journal
    of the American Chemical Society</i>. American Chemical Society, 2025. <a href="https://doi.org/10.1021/jacs.4c16050">https://doi.org/10.1021/jacs.4c16050</a>.
  ieee: L. Anghileri <i>et al.</i>, “Evidence for a unifying NiI/NiIII mechanism in
    light-mediated cross-coupling catalysis,” <i>Journal of the American Chemical
    Society</i>, vol. 147, no. 16. American Chemical Society, pp. 13169–13179, 2025.
  ista: Anghileri L, Baunis H, Bena A, Giannoudis C, Burke JH, Reischauer S, Merschjann
    C, Wallick RF, Al Said T, Adams CE, Simionato G, Kovalenko S, Dell’Amico L, Van
    Der Veen RM, Pieber B. 2025. Evidence for a unifying NiI/NiIII mechanism in light-mediated
    cross-coupling catalysis. Journal of the American Chemical Society. 147(16), 13169–13179.
  mla: Anghileri, Lucia, et al. “Evidence for a Unifying NiI/NiIII Mechanism in Light-Mediated
    Cross-Coupling Catalysis.” <i>Journal of the American Chemical Society</i>, vol.
    147, no. 16, American Chemical Society, 2025, pp. 13169–13179, doi:<a href="https://doi.org/10.1021/jacs.4c16050">10.1021/jacs.4c16050</a>.
  short: L. Anghileri, H. Baunis, A. Bena, C. Giannoudis, J.H. Burke, S. Reischauer,
    C. Merschjann, R.F. Wallick, T. Al Said, C.E. Adams, G. Simionato, S. Kovalenko,
    L. Dell’Amico, R.M. Van Der Veen, B. Pieber, Journal of the American Chemical
    Society 147 (2025) 13169–13179.
corr_author: '1'
date_created: 2025-04-20T22:01:28Z
date_published: 2025-04-11T00:00:00Z
date_updated: 2025-10-02T08:22:12Z
day: '11'
ddc:
- '540'
department:
- _id: BaPi
doi: 10.1021/jacs.4c16050
external_id:
  isi:
  - '001465858000001'
  pmid:
  - '40211781'
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has_accepted_license: '1'
intvolume: '       147'
isi: 1
issue: '16'
language:
- iso: eng
license: https://creativecommons.org/licenses/by/4.0/
month: '04'
oa: 1
oa_version: Published Version
page: 13169–13179
pmid: 1
project:
- _id: 8f1d607d-16d5-11f0-9cad-ab453295ba5e
  grant_number: PAT 1250924
  name: Photoactive ligands for transformative nickel catalysis
publication: Journal of the American Chemical Society
publication_identifier:
  eissn:
  - 1520-5126
  issn:
  - 0002-7863
publication_status: published
publisher: American Chemical Society
quality_controlled: '1'
scopus_import: '1'
status: public
title: Evidence for a unifying NiI/NiIII mechanism in light-mediated cross-coupling
  catalysis
tmp:
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  name: Creative Commons Attribution 4.0 International Public License (CC-BY 4.0)
  short: CC BY (4.0)
type: journal_article
user_id: 2DF688A6-F248-11E8-B48F-1D18A9856A87
volume: 147
year: '2025'
...