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

Qi Xu; Chenxi Guo; Beibei Li; Zedong Zhang; Yajun Qiu; Shubo Tian; Lirong Zheng; Lin Gu; Wensheng Yan; Dingsheng Wang; Jian Zhang

doi:10.1021/jacs.2c01456

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

J Am Chem Soc. 2022 Mar 16;144(10):4321-4326. doi: 10.1021/jacs.2c01456. Epub 2022 Mar 2.

Authors

Qi Xu¹, Chenxi Guo², Beibei Li¹, Zedong Zhang¹, Yajun Qiu¹, Shubo Tian³, Lirong Zheng⁴, Lin Gu⁵, Wensheng Yan⁶, Dingsheng Wang¹, Jian Zhang⁷

Affiliations

¹ Department of Chemistry, Tsinghua University, Beijing 100084, China.
² State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
³ State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, China.
⁴ Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China.
⁵ Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China.
⁶ National Synchrotron Radiation Laboratory, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, 230029 Hefei, China.
⁷ College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang 325035, China.

PMID: 35235317
DOI: 10.1021/jacs.2c01456

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 Al³⁺ doping strategy to construct single-atom Cu on MgO nanosheets (Cu₁/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). 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 ∼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.