4.8 Article

Al3+ Dopants Induced Mg2+ Vacancies Stabilizing Single-Atom Cu Catalyst for Efficient Free-Radical Hydrophosphinylation of Alkenes

Journal

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 144, Issue 10, Pages 4321-4326

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c01456

Keywords

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Funding

  1. National Key R&D Program of China [2018YFA0702003]
  2. National Natural Science Foundation of China [21890383, 22102119, 21871159, 52002249]
  3. Guangdong Basic and Applied Basic Research Foundation [2019A1515110025]
  4. Science and Technology Key Project of Guangdong Province of China [2020B010188002]
  5. National Postdoctoral Program for Innovative Talents [BX20190167]
  6. Shuimu Tsinghua Scholar Program
  7. China Postdoctoral Science Foundation [2020M670283]

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In this study, a doping strategy using Al3+ was successfully employed to construct single-atom Cu on MgO nanosheets (Cu-1/MgO(Al)) for promoting the free-radical hydrophosphinylation of alkenes. The Cu-1/MgO(Al) catalyst exhibited superior activity, durability, and anti-Markovnikov selectivity compared to Cu/MgO catalyst without Al3+ doping.
Utilizing heterogeneous catalysts to overcome obstacles for homogeneous reactions is fascinating but very challenging owing to the difficult fabrication of such catalysts based on the character of target reactions. Herein, we report a Al3+ doping strategy to construct single-atom Cu on MgO nanosheets (Cu-1/MgO(Al)) for boosting the free-radical hydrophosphinylation of alkenes. Al3+ dopants in MgO bring about abundant Mg2+ vacancies for stabilizing dense independent Cu atoms (6.3 wt %), while aggregated Cu nanoparticles are formed without Al3+ dopants (Cu/MgO). Cu-1/MgO(Al) exhibits preeminent activity and durability in the hydrophosphinylation of various alkenes with great anti-Markovnikov selectivity (99%). The turnover frequency (TOF) value reaches up to 1272 h(-1), exceeding those of Cu/MgO by similar to 6-fold and of traditional homogeneous catalysts drastically. Further experimental and theoretical studies disclose that the prominent performance of Cu-1/MgO(Al) derives from the accelerated initiating step of phosphinoyl radical triggered by individual Cu atoms.

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