Qi Xu+, Chenxi Guo+, Beibei Li, Zedong Zhang, Yajun Qiu, Shubo Tian, Lirong Zheng, Lin Gu, Wensheng Yan, Dingsheng Wang*, Jian Zhang*, Al3+ Dopants Induced Mg2+ Vacancies Stabilizing Single-Atom Cu Catalyst for Efficient Free-Radical Hydrophosphinylation of Alkenes

Release time:2023-05-20 Hits:

DOI number:10.1021/jacs.2c01456

Journal:Journal of the American Chemical Society

Abstract: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 Al(3+) doping strategy to construct single-atom Cu on MgO nanosheets (Cu1/MgO(Al)) for boosting the free-radical hydrophosphinylation of alkenes. Al(3+) dopants in MgO bring about abundant Mg(2+) vacancies for stabilizing dense independent Cu atoms (6.3 wt %), while aggregated Cu nanoparticles are formed without Al(3+) dopants (Cu/MgO). Cu1/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 approximately 6-fold and of traditional homogeneous catalysts drastically. Further experimental and theoretical studies disclose that the prominent performance of Cu1/MgO(Al) derives from the accelerated initiating step of phosphinoyl radical triggered by individual Cu atoms.

Indexed by:Journal paper

Discipline:Natural Science

Document Type:J

Volume:144

Page Number:4321-4326

Translation or Not:no

Date of Publication:2022-03-02

Included Journals:SCI

Links to published journals:https://pubs.acs.org/doi/10.1021/jacs.2c01456