Nickel(II) complexes of amine functionalized N-heterocyclic carbenes (NHCs), synthesis and catalysis in Kumada coupling of aryl chlorides

Article abstract of DOI:10.1016/j.jorganchem.2016.07.024

A new amine functionalized double chelate NHC nickel complex 2 was synthesized and characterized. Complexes 4a and 4b were generated through an improved synthetic method. Catalytic ability of the three nickel complexes were tested in Kumada coupling reaction. Complex 2 showed the best catalytic activity among them. With only 0.5?mol% of complex 2, the coupling of aryl chlorides with Grignard reagents received good yields.

Full text of DOI:10.1016/j.jorganchem.2016.07.024

Accepted Manuscript
Nickel(II) complexes of amine functionalized N-heterocyclic carbenes (NHCs),
synthesis and catalysis in Kumada coupling of aryl chlorides
Shumiao Zhang, Xiaoyan Li, Hongjian Sun, Olaf Fuhr, Dieter Fenske
PII:
S0022-328X(16)30317-5
10.1016/j.jorganchem.2016.07.024
JOM 19575
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 6 April 2016
Revised Date: 20 June 2016
Accepted Date: 29 July 2016
Please cite this article as: S. Zhang, X. Li, H. Sun, O. Fuhr, D. Fenske, Nickel(II) complexes of amine
functionalized N-heterocyclic carbenes (NHCs), synthesis and catalysis in Kumada coupling of aryl
chlorides, Journal of Organometallic Chemistry (2016), doi: 10.1016/j.jorganchem.2016.07.024.
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ACCEPTED MANUSCRIPT
Pictogram
________________________________________
Nickel(II) Complexes of Amine Functionalized N-Heterocyclic Carbenes (NHCs),
Synthesis and Catalysis in Kumada Coupling of Aryl Chlorides
Shumiao Zhang, aXiaoyan Li,a Hongjian Sun*,a, Olaf Fuhr,b Dieter Fenskeb
School of Chemistry and Chemical Engineering, Key Laboratory of Special Functional
Aggregated Materials, Ministry of Education, Shandong University, Shanda Nanlu 27,
250199 Jinan, PR China
N
iPr
N
iPr
Ni(PPh3)2Cl2
K2CO3, Py
N
N
H
Ni
N
N
N
N
N
Br
1
91% 2
0.5 mol% 2
Ar-Cl + Ar'-MgBr
Ar-Ar'
THF
76-99% isolated yields
1

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Nickel(II) Complexes of Amine Functionalized N-Heterocyclic Carbenes (NHCs),
Synthesis and Catalysis in Kumada Coupling of Aryl Chlorides
Shumiao Zhang,a Xiaoyan Li,a Hongjian Sun*,a, Olaf Fuhr,b Dieter Fenskeb
a
School of Chemistry and Chemical Engineering, Key Laboratory of Special
Functional Aggregated Materials, Ministry of Education, Shandong University,
Shanda Nanlu 27, 250199 Jinan, PR China,*E-mail: hjsun@sdu.edu.cn
b
Institutfür Nanotechnologie (INT) und Karlsruher Nano-Micro-Facility (KNMF),
Karlsruher Institutfür Technologie (KIT), Hermann-von-Helmholtz-Platz 1, 76344
Eggenstein-Leopoldshafen, Germany
Abstract
A new amine functionalized double chelate NHC nickel complex 2 was synthesized
and characterized. Complexes 4a and 4b were generated through an improved
synthetic method. Catalytic ability of the three nickel complexes were tested in
Kumada coupling reaction. Complex 2 showed the best catalytic activity among them.
With only 0.5 mol% of complex 2, the coupling of aryl chlorides with Grignard
reagents received good yields.
Keywords: Amine-fuctionalized; NHCs; Nickel; Kumada coupling
*Corresponding author. Tel.: + 86 531 88361350; Fax: + 86 531 88564464.
E-mail: hjsun@sdu.edu.cn.
1. Introduction
Transition metal complexes of N-heterocyclic carbene ligands are of great importance
in organometallic studies and catalytic application.1A significant component among
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the NHCs is the functionalized NHC ligands. Because of the diversity of functional
groups in the NHCs, the metal complexes could be pincer complexes2, bidentate
complexes3, sandwich or half-sandwich complexes4. Difference of the functional
groups brings up diverse character of the metal complexes, so they can catalyze
reactions such as Suzuki coupling2b,2g,5, Kumada coupling2j,6, hydrosilylation7, and
Heck reaction.3,8
The first amino NHC transition metal complex containing a secondary alky amine
moiety was reported by Douthwaite’s group9, and this kind of ligand was used for
synthesis of a series of palladium complexes10. The diarylamine functionalized NHC
ligand was first reported by Luo’s group5a. The palladium5a,11, nickel5b, platinum11,
and rare earth metal12 complexes were synthesized from this kind of ligand. The
NH/NH2 moieties inreported [C, N] type NHCs were mainly coordinated to the metal
center8a,7d,13 and in a few cases the NH protons could be deprotonated by bases11,14
.
Transition metal complexes of NHCs containing carbazide backbone were first
reported by Kunz’s group15. In the examples of amido NHC complexes16, the NH
protons were activated and the nitrogen atom was coordinated to the metal center to
form bidentate or tetradentate complexes.
Palladium and platinum aryl amine functionalized [C, N] type complexes were
reported previously. But nickel complex with this kind of ligand has not been studied.
Here we report a diarylamine functionalized [C, N] type NHC ligand. While
generating the nickel(II) complex, a double chelate homoleptic complex was obtained.
The nickel complex was proved to be efficient in Kumada coupling reactions of aryl
chlorides.
2. Results and Discussion
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Scheme 1 Preparation of 1
The preparation of ligand 1 is shown in Scheme 1. In the proton NMR spectrum of 1,
the amine proton and the NHC proton were appeared at 7.77 and 9.90 ppm
respectively. Reaction of ligand 1 with 0.5 equivalent Ni(PPh3)2Cl2 in pyridine, using
o
K2CO3 as base, at 90 C for 2 hours produced complex 2 in a yield of 91% (Scheme
2). In the proton NMR spectrum of complex 2, the aryl methyl group and the iPr
methyl groups in the two ligands showed up separately because the ligands were
blocked and the methyl groups orientated in different chemical environments. Red
crystal of complex 2 was obtained by slow evaporation of a mixture of CH2Cl2 and
petroleum ether. The structure was identified through X-ray crystallographic analysis
(Fig. 1). The configuration of central Ni is square-planar. The Ni-Ccarbene bond length
(C14-Ni1) is 1.865(2)Å and the Ni-Namine bond length (N1-Ni1) is 1.945(1)Å.
90ºC2h
Scheme 2 Preparation of nickel complex 2
3

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Fig. 1 Crystal structure of complex 2, 50% probability level, hydrogen atoms omitted.
Selected bond lengths (Å) and angles (deg): C14-Ni1 1.865(2), N1-Ni1 1.945(1),
C14-Ni1-N1a168.37(6),
C14-Ni1-C14a95.37(9).
C14a-Ni1-N1
168.37(6),
C14-Ni1-N1
84.70(6),
A new synthetic method for known complex 4a and 4b was carried out (Scheme 3).
Reaction of ligands 3a/3b with Ni(PPh3)2Cl2 using Et3N as base in THF for 36h
provided 4a/4b in the yields of 36%/37%. In the published synthetic pathway5b, Ag2O
was used to carry out the transmetalation. This is a traditional approach to obtain
NHC metal complexes. Our new method is a one-step reaction without using more
precious Ag. To synthesize these complexes (4a and 4b), we have tried a lot of
methods. Not only Et3N could be used in the process, nBuLi worked as well.
Comparing these methods with the transmetalation way, Et3N is the best reagent for
the reaction. The solvent is reusable in this case. This new method made the process
more convenient without losing yields. In the crystal structure of 4a (Fig. 2), the
Ni-Ccarbene bond length (C8-Ni1 = 1.902(3) Å) is longer than that (C14-Ni1 1.865(2) Å)
in complex 2 and the Ni-Namine bond length (N1-Ni1 1.891(4) Å) is shorter than that
(N1-Ni1 1.945(1) Å)in complex 2 due to the strong trans-influence of the Ccarbene
atom.
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Scheme 3 New synthetic method for complexes 4a and 4b.
Fig. 2 Crystal structure of complex 4a, 50% probability level, hydrogen atoms
omitted. Selected bond lengths (Å) and angles (deg): C8-Ni1 1.902(3), N1-Ni1
1.891(4), Ni1-Cl1 2.1847(19), C8-Ni1-N1 87.27(12), C8-Ni1-Cl1 92.73(12),
N1-Ni1-Cl1 180.0, C8-Ni1-C8a174.5(2).
With the three nickel complexes, we tested their catalytic property for Kumada
coupling reactions. As shown in Table 1, the reaction conditions were optimized by
coupling of 4-chloroanisole with phenylmagnesium bromide. At first, we added the
substrate in the order of catalyst, solvent, 4-chloroanisole and phenylmagnesium
bromide (entries 1-3, Table 1). It seems that higher temperature benefits the reaction
(entry 2, Table 1). In an accidental trial, phenylmagnesium bromide was added before
4-chloroanisole, the reaction completed in a conversion of 99% (entry 4, Table 1).
This phenomenon implies that the reaction rate of active Ni(0) species with substrates
is faster than the generation of Ni(0). If the Grignard reagent is added before aryl
chloride, it only reacts with the Ni(II) complex to generate Ni(0). If the Grignard
reagent is added after aryl chloride, once Ni(0) comes up, the competition begins and
consequently only part of the catalyst works during the tested time due to the
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unsatisfactory solubility of complex 2. Then the catalyst loading was reduced and the
o
temperature was set to be 40 C (entries 5-9, Table 1). The catalyst loading could be
lowered to 0.5 mol% to keep the conversion to 99%. Higher temperature was tried but
more homocoupling product of phenylmagnesium was found. DMSO and toluene
were also used as solvent (entries 10-11, Table 1). However, the result was not as
good as the reaction in THF. Complexes 4a and 4b showed poor catalytic ability
(entries 12-13, Table 1). Therefore, the best conditions for the Kumada coupling
o
reaction are 0.5 mol% of complex 2 as catalyst, reacting in THF at 40 C for 24h
(entry 7, Table1).
Table1 Optimization of reaction conditions for Kumada coupling reaction
T/℃
Cat./
mol%
1
Solvent
Conversion
Entry Cat.
/%a
30b
92b
64b
99
1
THF
THF
THF
THF
THF
THF
THF
THF
THF
toluene
DMSO
THF
THF
25
40
25
25
25
40
40
40
40
40
40
40
40
2
2
1
2
3
2
2
4
2
2
5
1
9
2
6
1
99
2
7
0.5
0.3
0.1
0.5
0.5
2
99
2
8
84
2
9
26
2
10
11
12
13
34
2
24
2
trace
15
4a
4b
2
6

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aGeneral condition: 1.0 mmol of aryl chloride, 1.5 mmol of Grignard reagent, 2 mL
THF, 24h. All the conversionswere determined by GC.
bAdd PhMgBr after 4-chloroanisole.
With the optimized reaction conditions, substrates were explored and shown in Table
2. Aryl chloride with -CF3 group in para-position gave a lower yield (5c and 5e,
Table 2). A sterically hindered group in aryl chloride has negative influence for the
reaction (5b and 5d, Table 2). 2-Naphthylmagnesium bromide went on the coupling
reaction almost quantitatively (5f and 5g, Table 2), while 2-pyridylmagnesium
bromide had a lower reaction activity (5h and 5i, Table 2). With dichlorides as
substrates,
p-dichlorobenzene
and
o-dichlorobenzene
generated
only
mono-substituted products (5j and 5l, Table 2). For m-dichlorobenzene, a mixture of
mono- and di-substituted products was detected under the general conditions. By
increasing the amount of Grignard reagent to 2.5 mmol and raising the catalyst
loading to 1 mol%, the corresponding m-terphenyl was obtained in 98% (5k, Table 2).
The results of Kumada coupling reactions using complex 2 as catalyst showed that the
catalyst loading is lower while the yields remain high comparing to those of the
catalysts with similar structures2d, 2j, 6b
.
Table 2 Kumada coupling of aryl chlorides with Grignard reagentsa
ArCl
Ar'MgBr
Products
5a
yields/%
99
88
84
87
5b
5c
5d
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98
85
99
5a
5e
5f
99
5g
82
76
90
98b
79
5h
5i
5j
5k
5l
aGeneral condition: 1.0 mmol of aryl chloride, 1.5 mmol of Grignard reagent, 0.005
mmol of complex 2, 2 mL THF, 40 oC, 24h. Isolated yields.
b2.5 mmol of Grignard reagent, 0.01 mmol of complex 2, di-substituted product
gained.
3. Conclusions
In conclusion, a new amine functionalized NHC nickel(II) complex 2 was generated.
Complexes 4a and 4b were synthesized in an improved method. Catalytic ability of
the three nickel complexes were tested in Kumada coupling reactions and complex 2
proved to be efficient with a catalyst loading of 0.5 mol%.
4. Experimental
General information. All the reactions for Kumada coupling and the reaction for
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synthesis of complex 4a were carried out using standard Schlenk techniques under
nitrogen atmosphere. THF and toluene were dried by Na using benzophenone as
indicator and distilled under N2. DMSO was dried by CaH2 and distilled under N2.
1
13
Other chemicals obtained commercially were used as received. H NMR, C NMR
were recorded on 300 MHz Bruker instrument. X-ray crystallography was carried out
on a Bruker Smart 1000 diffractometer. Elemental analyses were carried out on an
Elementar Vario ELIII instrument. High Resolution Mass Spectra were carried out
using Agilent 6510 (PLgel10um500A 300X25mm).
Synthesis of ligand 1. 2-Bromoaniline (1.00 g, 5.8 mmol) and
4-methylphenylboronic acid (0.82 g, 6.0 mmol) were put in a round bottom bottle.
Cu(OAc)2 (1.57 g, 8.7 mmol) was added as catalyst, then NEt3 (1.75 g, 17.4 mmol)
was added as base in 50 mL CH2Cl2. After stirring for 24h in room temperature,
2-bromo-N-(p-tolyl)aniline was separated through column chromatography with
petroleum ether : acetic ether 10:1 as eluent in a yield of 70%(1.06 g). The next step
was using 2-bromo-N-(p-tolyl)aniline (1.00 g, 3.8 mmol), imidazole (0.31 g, 4.6
mmol), K2CO3 (1.05 g, 7.6 mmol), CuO (0.03 g, 0.4 mmol), after dissolved in 20 mL
DMSO, the mixture was heated to 180°C for 3h. Water was added after cooling to
room temperature and CH2Cl2 was added to extract the product.
2-imidazole-N-(p-tolyl)aniline was gained through column chromatography with
acetic ether as eluent in a yield of 56%(0.53 g). The last step is
2-imidazole-N-(p-tolyl)aniline(1.00 g, 4.0 mmol) and iPrBr(0.49 g, 4.0 mmol) heated
to 90 °C in 20 mL MeCN in a sealed tube for 18h. Ligand 1 is obtained as brown
1
powder by removing the solvent in a yield of 95%(1.42 g). H NMR (300 MHz,
CDCl3) : 9.91 (1H, s), 7.77 (1H, s), 7.43 (1H, d, J=9.0 Hz), 7.37-7.34 (3H, m), 7.30
(1H, dd, J=9.0 Hz, 3.0 Hz), 7.14-7.10 (2H, m), 7.04-6.98 (3H, m), 4.90 (1H, m), 2.25
(3H, s), 1.63 (6H, d, J=9.0 Hz).13C NMR (300 MHz, CDCl3) :140.19, 139.75, 136.36,
131.26, 130.73, 129.65, 126.66, 125.43, 123.11, 121.63, 121.27, 119.74, 118.88,
53.54, 22.77, 20.69.
IR (ѵ, cm-1): 3192, 3149, 3057, 1598, 1562, 1517, 1377, 1317, 1205, 1110, 806, 746.
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Synthesis of complex 2 . Ligand 1 (0.15 g, 0.4 mmol), Ni(PPh3)2Cl2 (0.13 g, 0.2
mmol), and K2CO3 (0.28 g, 2.0 mmol) were put in a round bottom bottle, 5 mL
pyridine was added as solvent. The mixture was heated to 90oC for 2h. After cooling
to room temperature, pyridine was removed and CH2Cl2 was added to extract the
product. Complex 2 was gained as orange powder in a yield of 91%(0.128 g). Red
crystal of complex 2 is obtained by slow evaporation of the mixture of CH2Cl2 and
petroleum ether. Dec. > 173oC. IR (Nujol mull, cm-1): 3162, 3131, 1606, 1589, 1556,
1377, 1340, 724. 1H NMR (300 MHz, CD2Cl2): 7.62-7.38 (7H, m), 7.22 (4H, s), 6.87
(5H, m), 6.51 (4H, m), 3.90 (2H, m), 1.46 (3H,s), 1.30 (6H, d, J=6.0 Hz), 1.18 (3H,
s), 0.91 (6H, d, 6.0 Hz). Anal. Calcd for C38H40N6Ni (639.47 g/mol): C, 71.37; H,
6.30; N, 13.13. Found: C, 71.69; H, 6.27; N, 12.97. HRMS-ESI(m/z) Calcd
forC38H40N6Ni[M-H]: 637.2590; Found: 637.2562.
Synthesis of ligands 3a and 3b. Ligands 3a and 3b were synthesized according to
reference5a. 1H NMR of 3a (300 MHz, CDCl3) : 10.42 (2H, s), 8.46 (1H, s), 7.49-7.40
(8H, m), 7.38-7.35 (6H, m), 7.10-7.05 (6H, m), 5.74 (4H, s), 2.27 (6H, s). 1H NMR of
3b (300 MHz, CDCl3) :9.89 (2H, s), 7.78 (1H, s), 7.65 (2H, s), 7.48 (2H, s), 7.18-7.09
(6H, m), 4.46 (4H, t, J=7.5Hz), 2.31 (6H, s), 1.91 (4H, m), 1.40 (4H, m), 0.97 (6H, t,
J=7.5Hz).
Synthesis of complex 4a. 3a (0.12 g, 0.20 mmol) and Ni(PPh3)2Cl2 (0.13 g, 0.20
mmol) were put in a round bottom bottle. Then 20 mL THF was added to the mixture.
NEt3 (0.08 g, 0.25 mmol) was added. The mixture was stirred for 36h at room
temperature and the solution turned purple. The solvent was removed under pressure
and the rude product was purified through flash chromatography using CH2Cl2 as
eluent. The final product was obtained as purple powder in a yield of 36%. The purple
crystal of 4a was gained from slow evaporation of the mixture of CH2Cl2 and
petroleum ether. 1H NMR of 4a (300 MHz, CDCl3) : 7.42-7.39 (4H, m), 7.32 (2H, d,
J=2.1 Hz), 7.23-7.15 (8H, m), 6.79-6.74 (6H, m), 5.94 (2H, d, J=14.7 Hz), 5.97 (2H,
10

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d, J=15.0 Hz), 2.35 (6H, s).
13C NMR of 4a (300 MHz, CDCl3) :162.27, 140.64, 137.62, 132.45, 128.51, 128.03,
127.57, 127.27, 126.61, 124.07, 123.21, 119.52, 117.18, 53.64, 20.75. Calcd for
C34H30ClN5Ni (602.79 g/mol): C, 67.75; H, 5.02; N, 11.62. Found: C, 67.35; H, 5.27;
N, 11.30.
Synthesis of complex 4b. The synthetic procedure is the same as complex 4a. Purple
1
powder gained in a yield of 37%. H NMR of 4b (300 MHz, CDCl3) : 7.33 (2H, d,
J=3.0 Hz), 7.20 (2H, s), 6.95 (2H, d, J=3.0 Hz), 6.68 (4H, s), 4.63 (2H,m), 4.27 (2H,
m), 2.32 (6H, s), 2.01 (2H, m), 1.78 (2H, m), 1.32 (4H, m), 0.87 (6H, t, J=9.0 Hz).
13C NMR of 4b (300 MHz, CDCl3) : 161.58, 140.59, 132.04, 126.98, 126.28, 123.91,
122.89, 119.35, 116.69, 49.81, 33.55, 20.71, 19.72, 13.66. Calcd for C28H34ClN5Ni
(534.75 g/mol): C, 62.89; H, 6.41; N, 13.10. Found: C, 63.14; H, 6.46; N, 13.29.
X-ray structure determination and crystal data for complexes 2 and 4a.
Diffraction data were collected on a Bruker SMART Apex II CCD diffractometer
equipped with graphite-monochromated Mo-Kα radiation (λ = 0.71073 Å). The
structures were resolved by direct or Patterson methods with the SHELXS-97
program and were refined on F2 with SHELXTL. Hydrogen atoms were included in
calculated positions and were refined using a riding model. CCDC-1433108 (2) and
CCDC-1032787 (4a) contain the supplementary crystallographic data for this paper.
Copies of the data can be obtained free of charge on application to CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK (fax (+44) 1223-336-033; e-mail:
deposit@ccdc.cam.ac.uk).
Crystal data for complex 2 : C38H40N6Ni, Mr = 639.47 g/mol, monoclinic, space
group C2/c, a= 14.158 (2) Å, b = 15.170(2) Å, c = 15.835(2) Å, β = 108.111(1)°, V =
3232.5(6) Å3, T = 173 (2) K, Z = 4, Dc = 1.314 g/cm3, ꢀ = 0.637 mm−1. A total of
12458 reflections were collected, 3733 unique (Rint = 0.0252), R1 =0.0300 (for 3733
reflections with I > 2 sigma(I)), wR2 = 0.0754 (all data),CCDC No. 1433108.
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Crystal data for complex 4a : C34H30ClN5Ni, Mr = 602.79, monoclinic, space group
C2/c, a = 16.342(1) Å, b = 9.4476(6) Å, c = 18.8740(9) Å, β = 102.865(4)°, V =
2840.8(3) Å3, T = 296 (2) K, Z = 4, Dc = 1.409 g/cm3, ꢀ = 2.104 mm−1. A total of
6282 reflections were collected, 2237 unique (Rint = 0.0490), R1 =0.0492 (for 2237
reflections with I > 2 sigma(I)), wR2 = 0.1329 (all data), CCDC No. 1032787.
General procedure for Kumada coupling reactions. A Schlenk tube was charged
with nickel complex and changed the atmosphere into N2. Then THF (2 mL),
Grignard reagent (1.5 mmol) and aryl chloride (1.0 mmol) were added in order. The
tube was heated to 40 oC and stirred for 24h. After cooling to room temperature, 1 mL
water was added. The water phase was extracted by ether for 3 times (5 mL each time)
and the organic phase was collected. The products were obtained through column
chromatography using petroleum ether as eluent.
NMR data for coupling products.
1H NMR of 5a (300 MHz, CDCl3) : 7.57-7.49 (4H, m), 7.41 (2H, t, J=6.0 Hz), 7.30
(1H, m), 6.98 (2H, dt, J=9.0 Hz, 3.0Hz), 3.85 (3H, s).
1H NMR of 5b (300 MHz, CDCl3) : 7.44-7.39 (3H, m), 7.36-7.31 (3H, m), 7.27 (2H,
m), 7.24 (1H, m), 2.27 (3H, s).
1H NMR of 5c (300 MHz, CDCl3) : 7.69 (4H, s), 7.60 (2H, m), 7.50-7.37 (3H, m).
1H NMR of 5d (300 MHz, CDCl3) : 7.27-7.22 (6H, m), 6.95 (2H, m), 3.85 (3H, s),
2.28 (3H, s).
1H NMR of 5e (300 MHz, CDCl3) : 7.66 (4H, s), 7.54 (2H, dt, J=9.0 Hz, 3.0Hz), 7.00
(2H, dt, J=9.0 Hz, 3.0 Hz), 3.87 (3H, s).
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1H NMR of 5f (300 MHz, CDCl3) : 7.92-7.82 (3H, m), 7.55-7.39 (9H, m).
1H NMR of 5g (300 MHz, CDCl3) : 7.91 (2H, t, J=9.0 Hz), 7.83 (1H, d, J=9.0 Hz),
7.51-7.41 (6H, m), 7.03 (2H, dt, J=9.0 Hz, 3.0 Hz), 3.90 (3H, s).
1H NMR of 5h (300 MHz, CDCl3) : 8.65 (1H, dq, J=4.8Hz, 0.9 Hz), 7.95 (2H, dt,
J=9.0Hz, 3.0 Hz), 7.74-7.65 (2H, m), 7.19-7.15 (1H, m), 7.00 (2H, dt, J=9.0Hz,
3.0Hz), 3.86 (3H, s).
1H NMR of 5i (300 MHz, CDCl3) : 8.70 (1H, dt, J=3.8Hz, 1.2Hz), 8.01-7.97 (2H, m),
7.78-7.71 (2H, m), 7.51-7.38 (3H, m), 7.24-7.21 (1H, m).
1H NMR of 5j (300 MHz, CDCl3) : 7.55-7.45 (4H, m), 7.37 (2H, dt, J=9.0 Hz, 3.0
Hz), 6.97 (2H, dt, J=9.0 Hz, 3.0 Hz), 3.85 (3H, s).
1H NMR of 5k (300 MHz, CDCl3) : 7.72 (1H, s), 7.61-7.56 (4H, m), 7.50-7.47 (3H,
m), 7.00 (4H, dt, J=9.0 Hz, 3.0 Hz), 3.87 (6H, s).
1H NMR of 5l (300 MHz, CDCl3) : 7.52 (1H, m), 7.44-7.39 (2H, m), 7.35-7.27 (2H,
m), 7.24-7.19 (1H, m), 6.98 (2H, dt, J=9.0 Hz, 3.0 Hz), 3.85 (3H, s).
Supplementary material: Electronic Supplementary Information (ESI) available:
NMR spectra, crystallographic data for 2 CCDC 1433108 and 4a CCDC 1032787.
Acknowledgements
Support of this work by NSFC (No.s21572119/21272138 ) is gratefully
acknowledged.
References
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1 (a) M. Bierenstiel, E. D. Cross, Coord. Chem. Rev. 255 (2011) 574. (b) S.
D-González, N. Marion, S. P. Nolan, Chem. Rev. 109 (2009) 3612.
2 (a) S. W. Reilly, H. K. Box, G. R. Kuchenbeiser, R. J. Rubio, C. S. Letko, K. D.
Cousineau, T. K. Hollis, Tetrahedron Lett. 55 (2014) 6738. (b) K. Inamoto, J.-i.
Kuroda, E. Kwon, K. Hiroya, T. Doi, J.Organomet. Chem. 694 (2009) 389. (c)
N. Merle, K. W. Törnroos, V. R. Jensen, E. L. Roux, J.Organomet. Chem. 696
(2011) 1691. (d) K. D. M. MaGee, G. Travers, B. W. Skelton, M. Massi, A. D.
Payne, D. H. Brown, Aust. J. Chem. 65 (2012) 823. (e) A. A. Danopoulos, N.
Tsoureas, J. C. Green, M. B. Hursthouse, Chem. Commun. (2003) 756. (f) M.
H.-Juárez, M. Vaquero, E. Álvarez, V. Salazar, A. Suárez, Dalton Trans. 42
(2013) 351. (g) F. Godoy, C. Segarra, M. Poyatos, E. Peris, Organometallics 30
(2011) 684. (h) M. H.-Juárez, J. L.-Serrano, P. Lara, J. P. M-Cerón, M. Vaquero,
E. Álvarez, V. Salazar, A. Suárez, Chem. Eur. J. 21 (2015) 7540. (i) X. Zhang,
A. M. Wright, N. J. DeYonker, T. K. Hollis, N. I. Hammer, C. E. Webster, E. J.
Valente, Organometallics, 31 (2012) 1664. (j) Y. Sun, X. Li, H. Sun, Dalton
Trans. 43 (2014) 9410.
3 N. Tsoureas, A. A. Danopoulos, A. A. D. Tulloch, M. E. Light, Organometallics
22 (2003) 4750.
4 (a) J. M. S. Cardoso, B. Royo, Chem. Commun. 48 (2012) 4944. (b) H.-M. Sun,
D.-M. Hu, Y.-S. Wang, Q. Shen, Y. Zhang, J.Organomet. Chem. 692 (2007)
903. (c) C. Segarra, E. M.-Marzá, M. Benítez, J. A. Mata, E. Peris, Angew.
Chem. Int. Ed. 51 (2012) 10841.
5 (a) W. Wei, Y. Qin, M. Luo, P. Xia, M. S. Wong, Organometallics 27 (2008)
2268. (b) S. Wang, F. Ren, Y. Qiu, M. Luo, J.Organomet. Chem. 788 (2015) 27.
6 (a) K. Matsubara, K. Ueno, Y. Shibata, Organometallics 25 (2006) 3422. (b) Z.
Xi, B. Liu, W. Chen, J. Org. Chem. 73 (2008) 3954. (c) W.-J. Guo, Z.-X. Wang,
J. Org. Chem. 78 (2013) 1054.
7 (a) A. Zanardi, E. Peris, J. A. Mata, New. J. Chem. 32 (2008) 120. (b) T. Chen,
X-G Liu, M. Shi, Tetrahedron 63 (2007) 4874. (c) S. Kawabata, H. Tokura, H.
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ACCEPTED MANUSCRIPT
Chiyojima, M. Okamoto, S. Sakaguchi, Adv. Synth. Catal. 354 (2012) 807. (d)
M. V. Jiménez, J. J. P.-Torrente, M. I. Bartolomé, V. Gierz, F. J. Lahoz, L. A.
Oro, Organometallics 27 (2008) 224.
8 (a) C.-C. Tsai, W.-C. Shih, C.-H. Fang, C.-Y. Li, T.-G. Ong, G. P. A. Yap, J. Am.
Chem. Soc. 132 (2010) 11887. (b) I. Peñafiel, I. M. Pastor, M. Yus, Eur. J. Org.
Chem. (2012) 3151. (c) S. G. Fiddy, J. Evans, T. Neisius, M. A. Newton, N.
Tsoureas, A. A. D. Tulloch, A. A. Danopoulos, Chem. Eur. J. 13 (2007) 3652.
(d) D. J. Nielsen, K. J. Cavell, B. W. Skelton, A. H. White, Organometallics 25
(2006) 4850.
9 R. E. Douthwaite, J. Houghton, B. M. Kariuki, Chem. Commun. (2004) 698.
10J. Houghton, G. Dyson, R. E. Douthwaite, A. C. Whitwood, B. M. Kariuki,
Dalton Trans. (2007) 3065.
11W. B. Cross, C. G. Daly, R. L. Ackerman, I. R. George, K. Singh, Dalton Trans.
40 (2011) 495.
12X. Gu, X. Zhu, Y. Wei, S. Wang, S. Zhou, G. Zhang, X. Mu, Organometallics
33 (2014) 2372.
13(a) L. G. Bonnet, R. E. Douthwaite, R. Hodgson, J. Houghton, B. M. Kariuki,
S. Simonovic, Dalton Trans. (2004) 3528. (b) B. Ballarin, L. Busetto, M. C.
Cassani, C. Femoni, A. M. Ferrari, I. Miletto, G. Caputo, Dalton Trans. 41
(2012) 2445. (c) W. W. N. O., A. J. Lough, R. H. Morris, Organometallics 28
(2009) 6755. (d) Y.-P. Huang, C.-C. Tsai, W.-C. Shih, Y.-C. Chang, S.-T. Lin, G.
P. A. Yap, I. Chao, T.-G. Ong, Organometallics 28 (2009) 4316.
14(a) W. B. Cross, C. G. Daly, Y. Boutadla, K. Singh, Dalton Trans. 40 (2011)
9722. (b) H. Jong, B. O. Patrick, M. D. Fryzuk, Can. J. Chem. 86 (2008) 803.
15(a) A. Seyboldt, B. Wucher, M. Alles, F. Rominger, C. M.-Mössmer, D. Kunz,
J.Organomet. Chem. 775 (2015) 202. (b) E. Jürgens, B. Wucher, F. Rominger,
K. W. Törnroos, D. Kunz, Chem. Commun. 51 (2015) 1897. (c) M. Moser, B.
Wucher, D. Kunz, F. Rominger, Organometalics 26 (2007) 1024. (d) A.
Seyboldt, B. Wucher, S. Hohnstein, K. Eichele, F. Rominger, K. W. Törnroos,
D. Kunz, Organometallics 34 (2015) 2717.
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ACCEPTED MANUSCRIPT
16(a) K. V. Tan, J. L. Dutton, B. W. Skelton, D. J. D. Wilson, P. J. Barnard,
Organometallics 32 (2013) 1913. (b) Y. Unger, T. Strassner, J.Organomet.
Chem. 713 (2012) 203. (c) A. Kumar, L. P. Bheeter, M. K. Gangwar, J.-B.
Sortais, C. Darcel, P. Ghosh, J.Organomet. Chem. 786 (2015) 63. (d) S. Kumar,
A. Narayanan, M. N. Rao, M. M. Shaikh, P. Ghosh, J. Chem. Sci. 123 (2011)
791.
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Highlights:
Amine Functionalized N-Heterocyclic Carbenes (NHCs)
Coupling of Aryl Chlorides
>
Nickel complex
>
Kumada