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reductive elimination of the product are also characteristic for
this catalytic cycle.
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4. Conclusion
Summarizing, the encapsulation of CoIII(bpy)3 complexes into
silica nanoparticles by means of Stőber or water-in-oil micro-
emulsion techniques is the facial and efficient route for
synthesis of differently sized composite silica spheres as the
nanocatalysts in oxidative CH/NH cross-coupling. It is also worth
noting that both size and architecture of the nanoparticles
provide powerful tool for modification of the oxidation
potentials and catalytic activity of CoIII(bpy)3 inside the nano-
particles.
Comparative analysis of the catalytic efficiency and selectiv-
ity in the CH/NH cross-coupling highlights 50 nm sized CoIII
(bpy)3-doped silica nanoparticles synthesized by water-in-oil
microemulsion technique as the most promising nanocatalyst.
Very low leaching of CoIII(bpy)3 complexes from the silica matrix
within the catalytic cycle along with the high product’s yield is
important advantage of the nanocatalyst. Easy separation of the
nanoparticles after the catalytic cycle facilitates their multiple
reusing. The catalytic reaction is efficient at room temperatures
without the basic and/or oxidative additives commonly used in
CH/NH cross-coupling. Thus, the use of Co as more cheap and
abundant alternate to Rh, Pd[1] provides high catalytic efficiency
and selectivity in the oxidative CÀ H functionalization even at
low concentrations. The developed nanocatalysts have the
potential for new applications in cobalt-catalyzed carbon-
heteroatom coupling or other reactions.
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Experimental Section
Experimental Details see Supporting Information.
Acknowledgements
This work was supported by Russian Science Foundation grant no.
19-13-00016. The authors gratefully acknowledge the CSF-SAC
FRC KSC RAS for the spectral (NMR, ESR, UV, etc.) studies.
Conflict of Interest
The authors declare no conflict of interest.
Keywords: cobalt
·
oxidation
·
supported catalysts
·
heterogeneous catalysis · electrochemistry
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ChemCatChem 2019, 11, 1–11
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