Communication
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Table 3 Kumada cross-coupling reaction of aryl dichlorides with
Grignard reagents catalyzed by 5ba
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Entry
X
R3
Yieldb (%)
1
2
3
4
5
6
7
8
o-Cl
o-Cl
m-Cl
m-Cl
m-Cl
p-Cl
p-Cl
p-Cl
H
p-Me
H
p-Me
p-OMe
H
p-Me
o-Me
72
65
92
89
93
94
89
85
a 25 °C, 24 h, 3 mol% 5b, 0.5 mmol aryl dichloride, and 1.25 mmol
Grignard reagent. b Isolated yields.
8 (a) J. Berding, J. A. van Paridon, V. H. S. van Rixel and
E. Bouwman, Eur. J. Inorg. Chem., 2011, 2450;
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and M. G. Organ, Angew. Chem., Int. Ed., 2012, 51, 3314.
9 (a) A. J. Huckaba, B. Cao, T. K. Hollis, H. U. Valle,
J. T. Kelly, N. I. Hammer, A. G. Oliver and C. E. Webster,
Dalton Trans., 2013, 42, 8820; (b) A. R. Chianese,
S. E. Shaner, J. A. Tendler, D. M. Pudalov, D. Y. Shopov,
D. Kim, S. L. Rogers and A. Mo, Organometallics, 2012, 31,
7359.
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248, 2239; (b) K. Inamoto, J. Kuroda, K. Hiroya, Y. Noda,
M. Watanabe and T. Sakamoto, Organometallics, 2006, 25,
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Organometallics, 2008, 27, 2268; (d) M. Hernández-Juárez,
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converted to the corresponding terphenyls in good yields
(Table 3, entries 3–8).
In summary, three [CNN]-pincer nickel(II) complexes (5a–5c)
with NHC and amine as donors were designed and fully
characterized. X-ray crystallography shows that the NHC and
amine coordinate to the nickel centre in a pincer fashion to
form the five- and six-membered rings. With a catalyst loading
of 2 mol%, complex 5b displayed high activity and was
able to efficiently catalyze the cross-coupling of aryl chlorides
or dichlorides with aryl Grignard reagents under mild
conditions.
We gratefully acknowledge the support by NSF China no.
21072113 and Shandong ZR2010BZ002.
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9412 | Dalton Trans., 2014, 43, 9410–9413
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