期刊
ACS CATALYSIS
卷 11, 期 16, 页码 10190-10197出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.1c02129
关键词
dirhodium(II) complexes; bridging ligands; axial ligands; ortho-metalated; dehydrosilylation; vinylarenes; alkoxysilanes; vinylsilanes
资金
- National Natural Science Foundation of China
In this study, dirhodium(II) complexes were used as catalysts for the dehydrosilylation of vinylarenes with tertiary silanes, particularly alkoxysilanes. The catalytic method showed a broad substrate scope and good tolerance towards both electron-donating and electron-withdrawing substituents on the vinylarenes. Mechanistic studies suggested that a stable and rigid dirhodium(II) complex was formed with DPPP and P(OMe)3, acting as the active species for catalyzing the dehydrosilylation reaction. Control experiments supported the role of norbornene as the hydrogen acceptor in generating the key catalytic intermediate.
Herein, we describe dirhodium(II) complexes for the ortho-metalated 1,3-bis(diphenylphosphino)propane (DPPP)-catalyzed dehydrosilylation of vinylarenes with tertiary silanes, particularly alkoxysilanes. This catalytic method displays a broad substrate scope. Both electron-donating and electron-withdrawing substituents on the vinylarenes are well tolerated in this protocol. The dehydrosilylation reactions are compatible with a diverse range of tertiary silanes such as (EtO)(3)SiH, (TMSO)(2)MeSiH, (HSiMe2)(2)O, Et3SiH, and Ph3SiH. Mechanistic studies indicated that a mixture of Rh-2(OAc)(4), DPPP, and P(OMe)(3) provided a stable and rigid dirhodium(II) complex with ortho-metalated DPPP as the bridging ligand and the phosphonate as the axial ligand in the catalytic system. The structure of the dirhodium(II) complexes was also supported by X-ray crystal diffraction. Further experiments confirmed that the dirhodium(II) complexes may be the active species that catalyze the dehydrosilylation reaction. Control experiments showed that norbornene works as the hydrogen acceptor in the reaction and plays a crucial role in the generation of the key catalytic intermediate, a rhodium silicon species.
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