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COMMUNICATION
Journal Name
Conflicts of interest
DOI: 10.1039/C8CC04456B
There are no conflicts to declare.
Notes and references
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key C–Ni–Si bonding orbital during
potential surfaces of TS8
G‡ for TS3 and TS8 at 120 °C; (B) evolution of the
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For selected examples, see: (a) H. Wang, G. Lu, G. J.
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4
→
TS3; (C) electrostatic
.
i
addition, a repulsive interaction between Pr and SiMe3 is
observed in TS8-L2, which explains its higher energy relative to
TS8-L2. Conversely, for L2, L1 and L1, the electrostatics of
the NCH and C6F5 fragments are poorly matched due to the
relatively smaller N-substituents, which leads to the higher
energies of the corresponding transition states.
To summarize, we have presented a mechanistic study on
the Ni-catalyzed silylation and hydroarylation of arenes with
vinylsilanes by means of DFT calculations. The selectivity is
determined by the competition between C–Si and C–C
reductive elimination, and NHC ligands play a critical role in
differentiating the two pathways. The C–Si reductive
elimination involves the four-coordinate intermediate, and the
NHCs with less steric bulk favor the C–Si formation due to the
small repulsions between the aryl and the ligand. Conversely,
bulky NHCs in the T-shaped intermediate of the C–C reductive
elimination exhibit better electrostatic matching with the
substrate, thus promoting the C–C formation. The present
results will provide important implications for future design of
NHCs to control the selectivity.
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This work was supported by National Natural Science
Foundation of China (No. 21705075). The authors thank Dr.
Jian-Biao Liu for helpful discussion.
4 | J. Name., 2012, 00, 1-3
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