Cross-coupling of ArX with ArMgBr catalyzed by N-heterocyclic carbene-based nickel complexes

Article abstract of DOI:10.1021/jo302425x

N-Heterocyclic carbene-based pincer nickel complexes were synthesized and characterized. These complexes efficiently catalyze cross-coupling of aryl Grignard reagents with aryl chlorides or fluorides under mild conditions.

Full text of DOI:10.1021/jo302425x

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Article
Cross-Coupling of Ar-X (X= Cl, F) with ArMgBr Catalyzed
by N-Heterocyclic Carbene-based Nickel Complexes
Wang-Jun Guo, and Zhong-Xia Wang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/jo302425x • Publication Date (Web): 04 Jan 2013
Downloaded from http://pubs.acs.org on January 6, 2013
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Cross-Coupling of Ar-X (X= Cl, F) with ArMgBr Catalyzed by
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N-Heterocyclic Carbene-based Nickel Complexes
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WangꢀJun Guo and ZhongꢀXia Wang*
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CAS Key Laboratory of Soft Matter Chemistry and Department of Chemistry, University of
Science and Technology of China, Hefei, Anhui 230026, People’s Republic of China
Eꢀmail: zxwang@ustc.edu.cn
Abstract
NꢀHeterocyclic carbeneꢀbased pincer nickel complexes were synthesized and characterized.
These complexes efficiently catalyze crossꢀcoupling of aryl Grignard reagents with aryl
chlorides or fluorides under mild conditions.
Introduction
The Kumada crossꢀcoupling reaction has been extensively investigated and widely applied in
organic synthesis to construct carbonꢀcarbon bonds since its discovery in 1970s.1,2 Catalysts for
Kumada coupling reaction derived from transition metals such as nickel, palladium, copper,
iron and cobalt were developed.3 In the past decades, organic bromides and iodides were
widely used as the electrophiles in the Kumada reaction.2,4ꢀ10 In recent decade, organic
chlorides received much more attention due to their low cost in industrial processes and the
diversity of available compounds.11,12 For example, Herrmann et al. carried out crossꢀcoupling
of aryl chlorides with aryl Grignard reagents using Ni(acac)2ꢀNHC as the catalyst.13 Kambe et
al. reported that in the presence of 1,3ꢀbutadiene NiCl2 efficiently catalyzes crossꢀcoupling of
primary alkyl chlorides and alkyl Grignard reagents.14 We and other groups found that pincer
nickel complexes have good catalytic activity for the Kumada reactions of aryl, heteroaryl or
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vinyl chlorides.15 Hu and coꢀworkers showed that N,N,Nꢀpincer nickel complex is effective for
the coupling of alkyl halides and alkylmagnesium reagents.16 Some palladium, iron, cobalt and
copper complexes were also proven to be active for the Kumada coupling of chloroarenes.17
Compared with CꢀCl bond, CꢀF bond is more difficult to transform due to its thermal and
chemical stability. In recent years, transitionꢀmetalꢀcatalyzed activation and conversion of
organic fluorides attracted considerable attention. The conversion of organic fluorides is
important for the fundamental understanding of the reactivity of very stable bonds, selective
defluorination of aliphatic fluorides, crossꢀcoupling with aryl fluorides, and transformation of
polyꢀ or perfluorinated compounds to partially fluorinated compounds.18,19 Some
stoichiometric and catalytic CꢀF bond activation reactions have been reported, including
several transitionꢀmetalꢀcatalyzed crossꢀcoupling reactions of aryl fluorides.18,20,21
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In our studies on search for new catalyst systems for the activation of inert Cꢀheteroatom
bonds, we found that Nꢀheterocyclic carbeneꢀbased pincer nickel complexes can activate not
only aryl CꢀCl bonds but also aryl CꢀF bonds and lead to crossꢀcouplings with aryl Grignard
reagents efficiently. Herein we reported the results.
Results and discussion
Our studies on catalysis of P,N,Pꢀ and P,N,Nꢀpincer nickel complexes showed that the
complexes containing small chelate nickel rings, e.g. 4,5ꢀ and 4,6ꢀfused metal rings, exhibited
good catalytic activity for the Kumada coupling of aryl chlorides.15a,b In 2009 we reported
synthesis of Nꢀheterocyclic carbeneꢀbased pincer nickel complexes containing 5,6ꢀ and
6,6ꢀfused nickel rings and their catalysis in the crossꢀcoupling of aryl chlorides with
arylmagnesium or zinc reagents.15c In these studies, iminophosphoranyl groups were also
proven to be excellent coordination groups for the stabilization and catalytic properties of the
complexes. In order to examine the effect of small chelate ring in the NHCꢀbased pincer nickel
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catalyst systems and try to improve the catalytic properties of NHCꢀbased pincer nickel
complexes, we designed and synthesized new C,N,Nꢀpincer nickel complexes 3aꢀ3g (Scheme 1)
which involve 4,6ꢀfused nickel ring structures and iminophosphoranyl coordination groups.
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Scheme 1. Synthesis of complexes 3a-3g
N R
N
N R
N
Ph2PNHR1
CH2Cl2
X
X
N
P
N3
R1
Ph
N
1a R = Me, X = I
1b R = i-Pr, X = I
1c R = PhCH2, X = Br
Ph
2a-2g
H
N
R
X
N
(1) n-BuLi
Ni
N
N
P
(2) (DME)NiCl2
Ph
R1
Ph
3a-3g
a R = Me, R1 = p-MeC6H4, X = I
b R = i-Pr, R1 = p-MeC6H4, X = I
c R = PhCH2, R1 = p-MeC6H4, X = Br
d R = PhCH2, R1 = p-MeOC6H4, X = Br
e R = PhCH2, R1 = 2,6-i-Pr2C6H3, X = Br
f R = PhCH2, R1 = n-Pr, X = Br
g R = PhCH2, R1 = t-Bu, X = Br
The new Nꢀheterocyclic carbeneꢀbased nickel complexes were constructed by a twoꢀstep
process as shown in Scheme 1. The ligand precursors 2a-2g were prepared by reaction of 115c
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with R1NHPPh2 in CH2Cl2. Treatment of 2a-2g with nꢀBuLi and subsequent (DME)NiCl2
generated nickel complexes 3aꢀ3g. Compounds 2a-2g, 3aꢀ3e and 3g were characterized by 1H,
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13C and P NMR spectroscopy and elemental analyses. Complex 3f is paramagnetic and was
characterized by elemental analysis and IR spectroscopy. The single crystal Xꢀray diffraction of
complex 3e confirmed a pincer coordination mode (Figure 1).
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Figure 1 ORTEP drawing of complex 3e (30% probability thermal ellipsoids).
Firstly, the catalysis of complexes 3aꢀ3g was evaluated using the crossꢀcoupling of
pꢀchloroanisole and pꢀtolylmagnesium bromide in THF at room temperature as the model
reaction (Table 1). 3b, 3c and 3d showed the highest catalytic activity and 3e exhibited the
lowest activity (entries 1ꢀ3 and 9ꢀ12, Table 1). The activity order is approximately 3b ≈ 3c ≈
3d > 3a ≈ 3f > 3g > 3e. It seems that very bulky R1 groups hinder catalysis of the complexes,
whereas influence of electronic effect of R1 groups on the catalytic property of the complexes
is negligible. Except 3e, each of these complexes shows higher catalytic activity than the
NHCꢀbased pincer nickel complexes containing 5,6ꢀ and 6,6ꢀfused metal rings we reported
previously.15c Activity of complexes 3b, 3c and 3d is also higher than most reported
nickelꢀbased catalysts for the Kumada coupling of deactivated chloroarenes, and comparable to
those of P,N,Oꢀpincer nickels 4 and 5 (Scheme 2)15d and bimetallic nickel complex 6 (Scheme
2).23 We also tested the reaction in other solvents using 3c. The results showed that toluene,
Et2O, 1,4ꢀdioxane and 1:1 mixture of THF and toluene were less effective in comparison with
THF (entries 4ꢀ7, Table 1). The catalytic reaction run in DME did not give crossꢀcoupling
product (entry 8, Table 1).
Table 1 Evaluation of catalytic activity of complexes 3a-3ga
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OMe
Cl
MgBr
cat.
+
MeO
Me
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7
Me
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9
Entry Complex
Solvent
Yieldb (%)
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1
THF
75
86
87
67
31
30
80
ꢀ
3a
3b
3c
3c
3c
3c
3c
3c
3d
3e
3f
2
THF
3
THF
4
Toluene
Et2O
5
6
1,4ꢀdioxane
THF/toluene (1:1)
DME
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9
THF
86
31
75
70
10
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12
THF
THF
THF
3g
a The reactions were carried out at 25 °C for 24 h in the presence of 1 mol% catalyst, 0.5
b
mmol pꢀClC6H4OMe and 0.75 mmol pꢀMeC6H4MgBr were employed. Isolated product
yields.
Scheme 2.
Ph2
P
Ph2
P
Cl
O
Ni
Cl
Ni
PPh2
N
N
O
PPh2
Ph
Ph
4
5
2+
N
N
N N
N
N
Ni
Ni
O
H
6
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Next we examined substrate scope using 3c as the catalyst (Table 2). The reaction between
C6H5Cl and pꢀMeC6H4MgBr afforded crossꢀcoupling product in nearly quantitative yield at
room temperature for 12 h using 1 mol% 3c (entry 1, Table 2). The deactivated aryl chlorides
including oꢀMeOC6H4Cl and 2,4ꢀMe2C6H3Cl also reacted with pꢀMeC6H4MgBr at room
temperature (entries 2 and 3, Table 2). However, higher catalyst loadings were required due to
steric hindrance of the chlorides, 5 mol% 3c for oꢀMeOC6H4Cl and 2 mol% 3c for
2,4ꢀMe2C6H3Cl. When temperature of reaction between oꢀMeOC6H4Cl and pꢀMeC6H4MgBr
was raised to 70 °C, the catalyst loading could be decreased to 2 mol% and the product yield
increased to 82%. Reaction of activated aryl chlorides including pꢀNCC6H4Cl, oꢀNCC6H4Cl
and pꢀEt2NC(O)C6H4Cl with pꢀMeC6H4MgBr proceeded smoothly and gave excellent yields
(entries 4ꢀ6, Table 2). The functional groups CN and Et2NC(O) were tolerated. Reaction of
2ꢀchloropyridine with pꢀMeC6H4MgBr in THF in the presence of 3c gave only moderate yield.
However, the reaction in Et2O led to excellent result. Sterically hindered Grignard reagent,
oꢀMeC6H4MgBr, showed lower reactivity than pꢀMeC6H4MgBr. Reaction of oꢀMeC6H4MgBr
with aryl chlorides including pꢀMeOC6H4Cl, pꢀNCC6H4Cl, oꢀNCC6H4Cl and 2ꢀClC5H4N gave
a little lower product yields compared with corresponding those using pꢀMeC6H4MgBr as the
nucleophilic species. 2 Mol% catalyst loadings were also necessary to complete the reaction
between oꢀMeC6H4MgBr and oꢀNCC6H4Cl. Electronꢀrich Grignard reagents pꢀMeOC6H4MgBr
and pꢀMe2NC6H4MgBr exhibited good reactivity with aryl chlorides in the presence of 3c.
However, their reactions with deactivated or sterically hindered aryl chlorides required
elevated temperature. For example, reaction of pꢀMeOC6H4MgBr with oꢀMeC6H4Cl was
carried out at 70 °C in the presence of 1 mol% 3c, leading to crossꢀcoupling product in 99%
yield (entry 15, Table 2). Reaction of pꢀMe2NC6H4MgBr with oꢀMeOC6H4Cl at 70 °C in the
presence of 2 mol% 3c gave 72% yield of pꢀ(oꢀMeOC6H4)C6H4NMe2 (entry 22, Table 2). In
addition, both pꢀMeOC6H4MgBr and pꢀMe2NC6H4MgBr were incompatible with pꢀNCC6H4Cl
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or oꢀNCC6H4Cl. Reaction between them in the presence of 3c resulted in addition products.
Whereas reaction of 2ꢀClC5H4N with either pꢀMeOC6H4MgBr or pꢀMe2NC6H4MgBr using 1
mol% 3c as catalyst formed crossꢀcoupling products in excellent yields (entries 16 and 24,
Table 2).
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Table 2 Cross-coupling of arylmagnesium bromides with aryl chlorides catalyzed by 3ca
3c
Ar-Ar1
+
ArMgBr
Ar1Cl
THF
Entry
Ar
Ar1Cl
Amount of
cat. (mol%)
1
Time/h
Yieldb (%)
1
pꢀMeC6H4
pꢀMeC6H4
pꢀMeC6H4
pꢀMeC6H4
pꢀMeC6H4
pꢀMeC6H4
pꢀMeC6H4
oꢀMeC6H4
oꢀMeC6H4
oꢀMeC6H4
oꢀMeC6H4
oꢀMeC6H4
C6H5Cl
12
24
24
14.5
17
13
12
24
24
14
24
12
12
24
17
12
24
24
12
12
12
24
98
73(82c,d)
2
oꢀMeOC6H4Cl
2,4ꢀMe2C6H3Cl
pꢀNCC6H4Cl
oꢀNCC6H4Cl
5
2
1
1
3
90
4
97
5
98
6
pꢀEt2NC(O)C6H4Cl 3
92
7
2ꢀClC5H4N
C6H5Cl
0.5
64(91e)
63(94c,f)
81
8
1
1
1
2
1
1
1
1
1
2
9
pꢀMeOC6H4Cl
pꢀNCC6H4Cl
oꢀNCC6H4Cl
2ꢀClC5H4N
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11
12
13
14
15
16
17
18
19
20
21
22
93
91
89e
pꢀMeOC6H4 C6H5Cl
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pꢀMeOC6H4 pꢀMeC6H4Cl
pꢀMeOC6H4 oꢀMeC6H4Cl
pꢀMeOC6H4 2ꢀClC5H4N
pꢀMeOC6H4 2,4ꢀMe2C6H3Cl
93c
99c
93
97
pꢀMeOC6H4 pꢀEt2NC(O)C6H4Cl 5
78
pꢀMe2NC6H4 C6H5Cl
1
1
1
2
91
pꢀMe2NC6H4 oꢀMeC6H4Cl
pꢀMe2NC6H4 pꢀMeC6H4Cl
pꢀMe2NC6H4 oꢀMeOC6H4Cl
97c
85c
72c
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25
pꢀMe2NC6H4 pꢀMeOC6H4Cl
1
1
1
24
12
19
96c
97
pꢀMe2NC6H4 2ꢀClC5H4N
pꢀMe2NC6H4 2,4ꢀMe2C6H3Cl
92
a Unless otherwise specified, the reactions were carried out on a 0.5 mmol scale and run
b
c
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d
e
run at 70 °C. The reaction was run for 22 h with 2 mol% catalyst. The reaction was
run in diethyl ether. f The reaction time was 12 h.
Complex 3c also exhibited good catalytic activity for the activation of aryl CꢀF bonds as
shown in Table 3. Activated, unactivated and deactivated aryl fluorides including PhF,
1ꢀFC10H7, pꢀMeOC6H4F, pꢀEt2NC(O)C6H4F and 2ꢀFC5H4N reacted efficiently with
pꢀMeC6H4MgBr, pꢀMeOC6H4MgBr or pꢀMe2NC6H4MgBr at room temperature in the presence
of 3c. For example, reaction of deactivated aryl fluoride, pꢀMeOC6H4F, with pꢀMeC6H4MgBr
proceeded smoothly. 2 Mol% loadings of 3c led to 91% product yield. This reaction could be
further improved by using a little higher catalyst loadings. 3 Mol% of 3c resulted in 99%
product yield (entries 2 and 3, Table 3). However, 3cꢀcatalyzed reaction of 3,4ꢀ(MeO)2C6H3F
with Grignard reagents required elevated temperature and gave only moderate product yields
(entries 7, 13 and 19, Table 3). pꢀFC6H4CH2OH also reacted efficiently with the Grignard
reagents mentioned above when excess Grignard reagents were employed. pꢀEt2NC(O)C6H4F
could couple with pꢀMeC6H4MgBr and pꢀMeOC6H4MgBr, respectively, when 8ꢀ10 mol% of 3c
were used as catalyst (entries 5 and 12, Table 3). Whereas reaction of pꢀMe2NC6H4MgBr with
pꢀEt2NC(O)C6H4F resulted in addition product. Reaction of pꢀFC6H4CN and oꢀFC6H4CN with
various Grignard reagents also afforded addition products. oꢀMeC6H4MgBr also reacted with
aryl fluorides using 3c as the catalyst, but showed lower reactivity in comparison with
pꢀMeC6H4MgBr. Reactions of oꢀMeC6H4MgBr with activated, unactivated and deactivated aryl
fluorides required elevated temperature, giving mederate to excellent product yields (entries
21ꢀ23, Table 3). Compared with the known nickel catalysts for the coupling of aryl fluorides
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and Grignard reagents, 3c shows higher activity than the Ni(II)/phosphine, Ni(II)/IPr and
Ni(II)/phosphine
oxide
systems,21eꢀh
but
lower
activity
than
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8
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Ni(acac)2/2ꢀ(Ph2P)C6H4CH(OH)Me system.21d The high activity of the latter is ascribed to a
cooperative pushꢀpull action of the nucleophilic nickel and Lewis acidic magnesium centers
based on experimental and computational studies.21d
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Table 3. Reaction of aryl fluorides with aryl Grignard reagents catalyzed by 3ca
3c
Ar-Ar1
ArMgBr
+
Ar1F
THF
Entry
Ar
Ar1F
Amount of
cat. (mol%)
2
Time/h
Yieldb (%)
1
pꢀMeC6H4
pꢀMeC6H4
pꢀMeC6H4
pꢀMeC6H4
pꢀMeC6H4
pꢀMeC6H4
pꢀMeC6H4
pꢀMeC6H4
C6H5F
24
24
24
12
24
12
24
12
17
12
11
24
24
12
12
12
24
12
24
12
99
2
pꢀMeOC6H4F
pꢀMeOC6H4F
1ꢀFC10H7
2
3
4
91
3
99
4
95
5
pꢀEt2NC(O)C6H4F 8
92
6
2ꢀFC5H4N
2
4
4
2
4
2
91
7
3,4ꢀ(MeO)2C6H3F
pꢀFC6H4CH2OH
74c
96d
99
8
9
pꢀMeOC6H4 C6H5F
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11
12
13
14
15
16
17
18
19
20
pꢀMeOC6H4 1ꢀFC10H7
pꢀMeOC6H4 2ꢀFC5H4N
86
95
pꢀMeOC6H4 pꢀEt2NC(O)C6H4F 10
74
pꢀMeOC6H4 3,4ꢀ(MeO)2C6H3F
pꢀMeOC6H4 pꢀFC6H4CH2OH
pꢀMe2NC6H4 C6H5F
4
4
2
4
2
2
4
4
72c
88c,d
92
pꢀMe2NC6H4 1ꢀFC10H7
95
pꢀMe2NC6H4 pꢀMeOC6H4F
pꢀMe2NC6H4 2ꢀFC5H4N
94
92
pꢀMe2NC6H4 3,4ꢀ(MeO)2C6H3F
pꢀMe2NC6H4 4ꢀFC6H4CH2OH
66c
86c,d
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oꢀMeC6H4
oꢀMeC6H4
oꢀMeC6H4
C6H5F
3
3
4
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24
12
92c
76c
69c
pꢀMeOC6H4F
2ꢀFC5H4N
a Unless otherwise specified the reactions were carried out on a 0.5 mmol scale and run
at 25 °C, 1.5 equiv. of ArMgBr were used. Isolated product yields. c The reaction was
b
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run at 70 °C. d 3 equiv. of ArMgBr were used.
Reactions of difluorobenzenes with Grignard reagents at room temperature catalyzed by
complex 3c were also carried out (Table 4). Treatment of 1,4ꢀdifluorobenzene with 3 equiv. of
pꢀMeC6H4MgBr, pꢀMeOC6H4MgBr, or pꢀMe2NC6H4MgBr in the presence of 4 mol% 3c at
room temperature gave 1,4ꢀbis(pꢀtolyl)benzene, 1,4ꢀdi(pꢀmethoxyphenyl)benzene and
1,4ꢀbis(pꢀdimethylaminophenyl)benzene, respectively, in nearly quantitative yields (entries 1, 4
and 5, Table 4). A similar reaction using oꢀMeC6H4MgBr required 5 mol% of 3c and elevated
temperature (70 °C) and gave the crossꢀcoupling product in 82% yield (entry 3, Table 4).
Reaction of 1,2ꢀdifluorobenzene with 3 equiv. of pꢀMeC6H4MgBr or pꢀMe2NC6H4MgBr in the
presence of 5 mol% 3c at 70 oC generated the crossꢀcoupling products in 82% and 95% yields,
respectively (entries 2 and 6, Table 3). It seems that the steric hindrance of 1,2ꢀdifluorobenzene
hinders the reaction to some extent and hence the reactions required elevated temperature and
higher catalyst loadings.
Table 4 Reaction of arylmagnesium reagents with difluorobenzene catalyzed by 3ca
F
Ar
3c
2 ArMgBr
F
Ar
THF
Entry
Ar
ArF2
Amount of
cat. (mol%)
4
Time/h
Yield b (%)
1
2
pꢀMeC6H4
pꢀMeC6H4
1,4ꢀF2C6H4
1,2ꢀF2C6H4
13
12
97
82c
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oꢀMeC6H4
1,4ꢀF2C6H4
5
4
4
5
22
12
12
12
85c
99
pꢀMeOC6H4 1,4ꢀF2C6H4
pꢀMe2NC6H4 1,4ꢀF2C6H4
pꢀMe2NC6H4 1,2ꢀF2C6H4
99
95c
a Unless otherwise specified the reactions were carried out on a 0.5 mmol scale and
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b
c
run at 25 °C, 3 equiv. of ArMgBr were used. Isolated product yields. The
reaction was run at 70 °C.
Conclusion
In summary, we have developed new NHCꢀbased nickel complex catalysts for the Kumada
reaction of aryl chlorides and fluorides. Complex 3c displayed high activity and is able to
catalyze crossꢀcoupling of activated, unactivated and deactivated chloroaromatics and
fluoroaromatics efficiently with aryl Grignard reagents under mild conditions.
Experimental section
The reactions were performed under nitrogen atmosphere. Solvents were distilled under
nitrogen over sodium (toluene and 1,4ꢀdioxane), sodium/benzophenone (THF, Et2O and DME)
or CaH2 (CH2Cl2) and degassed prior to use. nꢀBuLi, CDCl3, aryl chlorides and fluorides were
purchased from commercial venders and used as received. 1aꢀ1c,15c R1NHPPh2,22
(DME)NiCl2 and aryl Grignard reagents25 were prepared according to the reported methods.
24
NMR spectra were determined on a 300 MHz NMR spectrometer at room temperature using
CDCl3 as solvent. The chemical shifts of the 1H and 13C NMR spectra were referenced to TMS
or internal solvent resonances, and the 31P NMR spectra were referenced to external 85%
H3PO4. Infrared (IR) spectra were recorded in the range 4000ꢀ600 cm−1 as KBr pellets.
Highꢀresolution mass spectra (HRMS) were acquired in the electron impact mode (EI) using a
TOF mass analyzer. Elemental analyses were performed by the Analytical Center of University
of Science and Technology of China.
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[o-(4-MeC6H4NHP(Ph2)=N)C6H4N(CH)2N(Me)CH]+I−
3
4
Synthesis
of
(2a).
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pꢀMeC6H4NHPPh2 (0.91 g, 3.11 mmol) was dissolved in CH2Cl2 (10 mL) and then cooled to
0 °C. To the solution was added a solution of 1a (0.95 g, 2.90 mmol) in CH2Cl2 (10 mL). The
mixture was warmed to room temperature and stirred overnight. The solution was filtered and
then about half volume of CH2Cl2 was removed from the filtrate. Diethyl ether (30 mL) was
added. Yellowish precipitates were formed from the the mixture. The precipitates were
collected by filtration, washed with diethyl ether (15 mL×2), and dried in vacuo to give a
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yellowish powder of 2a⋅0.17CH2Cl2⋅0.35Et2O (1.47 g, 80%), m.p. 123ꢀ124 °C. H NMR: δ
1.20 (t, J = 6.9 Hz, Et2O), 2.17 (s, 3H), 3.48 (q, J = 6.9 Hz, Et2O), 4.00 (s, 3H), 5.29 (s, 0.35H,
CH2Cl2), 6.26 (b, 1H), 6.74 (t, J = 7.5 Hz ,1H), 6.87ꢀ7.09 (m, 6H), 7.33ꢀ7.37 (m, 1H),
7.42ꢀ7.53 (m, 7H), 7.63 (s, 1H), 7.74ꢀ7.81 (m, 4H), 9.59 (s, 1H). 13C NMR: δ 15.3, 20.7, 37.2,
65.9, 119.2, 119.3, 122.5, 123.6, 124.5, 125.2, 129.3 (d, J = 13.1 Hz), 129.8, 131.0, 131.8,
131.9, 132.1, 132.7, 136.9, 137.3. 31P NMR: δ −0.20. Anal. Calcd. for C29H28IN4P: C, 58.99; H,
4.80; N, 9.49%. Found: C, 58.49; H, 5.19; N, 9.32%. (The sample for elemental analysis was
recrystallized from CH2Cl2).
Synthesis
of
[o-(4-MeC6H4NHP(Ph2)=N)C6H4N(CH)2N(i-Pr)CH]+I−
(2b).
pꢀMeC6H4NHPPh2 (0.71 g, 2.44 mmol) was dissolved in CH2Cl2 (10 mL) and then cooled to
0 °C. To the solution was added a solution of 1b (0.72 g, 2.03 mmol) in CH2Cl2 (10 mL). The
resulting mixture was warmed to room temperature and stirred overnight. The solution was
filtered and the filtrate was concentrated to about half of the original volume. Diethyl ether (30
mL) was added. Yellowish precipitates were formed. The precipitates were collected by
filtration, washed with diethyl ether (15 mL×2), and dried in vacuo to give a yellowish powder
of 2b⋅0.16CH2Cl2⋅0.5Et2O (1.20 g, 84%), m.p. 123ꢀ124 °C. 1H NMR: δ 1.20 (t, J = 7.2 Hz, 3H,
Et2O), 1.56 (d, J = 6.6 Hz, 6H), 2.16 (d, 3H), 3.48 (q, J = 7.2 Hz, 2H, Et2O), 5.04ꢀ5.18 (m, 1H),
5.29 (s, 0.31H, CH2Cl2), 6.39 (b, 1H), 6.71ꢀ6.82 (m, 1H), 6.89 (d, J = 8.2 Hz, 2H), 6.98 (d, J =
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8.2 Hz, 2H), 7.05 (d, J = 3.9 Hz, 2H), 7.35ꢀ7.55 (m, 8H), 7.75ꢀ7.81 (m, 4H), 7.86 (s, 1H), 9.48
(s, 1H). 13C NMR: δ 15.3, 20.6, 23.2, 53.3, 65.9, 119.1, 119.5, 119.6, 123.8, 124.1, 125.2,
128.7, 128.9, 129.2 (d, J = 13.1 Hz), 129.8, 130.9, 131.9 (d, J = 10 Hz), 132.7, 134.8, 137.3.
31P NMR: δ 0.26. Anal. Calcd. for C31H32IN4P: C, 60.20; H, 5.22; N, 9.06%. Found: C, 60.40;
H, 5.49; N, 8.91%. (The sample for elemental analysis was recrystallized from CH2Cl2).
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Synthesis
of
[o-(4-MeC6H4NHP(Ph2)=N)C6H4N(CH)2N(Bn)CH]+Br−
(2c).
pꢀMeC6H4NHPPh2 (1.70 g, 5.85 mmol) was dissolved in CH2Cl2 (10 mL) and cooled to 0 °C.
To the solution was added a solution of 1c (1.95 g, 5.47 mmol) in CH2Cl2 (10 mL). The
mixture was warmed to room temperature and stirred overnight. The resulting solution was
filtered and the filtrate was concentrated to afford a pale yellow powder of 2c⋅0.33CH2Cl2
(3.05 g, 88%), m.p. 132ꢀ133 °C. 1H NMR: δ 2.16 (s, 3H), 5.29 (s, 0.67H, CH2Cl2), 5.63 (s, 2H),
6.41 (d, J = 9 Hz, 1H), 6.73 (t, J = 7.5 Hz, 1H), 6.83ꢀ6.93 (m, 5H), 7.00ꢀ7.05 (m, 1H),
13
7.25ꢀ7.33 (m, 4H), 7.36ꢀ7.51 (m, 10H), 7.71ꢀ7.78 (m, 4H), 10.14 (s, 1H). C NMR: δ 20.7,
53.4, 118.5, 119.3 (d, J = 6 Hz), 120.8, 123.6, 124.1 (d, J = 9.7 Hz), 125.2, 129.1, 129.2, 129.3,
129.4, 129.8, 130.9, 131.5, 131.9, 132.4 (d, J = 2.3 Hz), 133.5, 136.9, 137.7. 31P NMR: δ −0.97.
Anal. Calcd. for C35H32BrN4Pꢁ0.5CH2Cl2: C, 64.41; H, 5.02; N, 8.46%. Found: C, 64.73; H,
5.22; N, 8.77%. (The sample for elemental analysis was recrystallized from CH2Cl2).
Synthesis
of
[o-(4-MeOC6H4NHP(Ph2)=N)C6H4N(CH)2N(Bn)CH]+Br−
(2d)
pꢀMeOC6H4NHPPh2 (0.76 g, 2.47 mmol) was dissolved in CH2Cl2 (10 mL) and cooled to 0 °C.
To the solution was added a solution of 1c (0.74 g, 2.08 mmol) in CH2Cl2 (10 mL). The
mixture was warmed to room temperature and stirred overnight. The resulting solution was
filtered and the filtrate was concentrated to about half of the volume. Diethyl ether (30 mL)
was added. Yellowish precipitates were formed. The precipitates were collected by filtration,
washed with diethyl ether (15 mL×2), and dried in vacuo to give a yellowish powder of
1
2dꢁ0.16CH2Cl2ꢁ0.46Et2O (1.30 g, 91%), m.p. 119ꢀ120 °C. H NMR: δ 1.20 (t, J = 6.9 Hz,
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2.82H, Et2O), 3.47 (q, J = 6.9 Hz, 1.84H, Et2O), 3.63 (s, 3H), 5.29 (s, 0.32H, CH2Cl2), 5.64 (s,
2H), 6.58 (d, J = 9 Hz, 3H), 6.69 (t, J = 7.2 Hz, 1H), 6.91ꢀ7.03 (m, 4H), 7.27ꢀ7.31 (m, 4H),
7.34ꢀ7.48 (m, 9H), 7.73ꢀ7.80 (m, 4H), 10.12 (s, 1H). 13C NMR: δ 15.4, 53.3, 55.5, 65.9, 114.5,
118.3, 120.8, 121.6 (d, J = 5.7 Hz), 123.6, 123.9, 124.0, 125.1, 129.0, 129.2, 129.3, 129.4,
130.9, 132.0, 132.2, 132.3 (d, J = 2.3 Hz), 133.2, 133.5, 136.9, 155.2. 31P NMR: δ 0.50.
Anal.Calcd. for C35H32BrN4POꢁ0.2Et2O: C, 66.11; H, 5.27; N, 8.61%. Found: C, 66.56; H, 5.57;
N, 8.64%. (The sample for elemental analysis was further purified. Thus, the crude product
was dissolved in CH2Cl2. The solution was added Et2O to form precipitate of 2d).
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Synthesis
of
[o-(2,6-i-Pr2C6H3NHP(Ph2)=N)C6H4N(CH)2N(Bn)CH]+Br−
(2e).
2,6ꢀiꢀPr2C6H3NHPPh2 (1.58 g, 4.37 mmol) was dissolved in CH2Cl2 (10 mL) and cooled to
0 °C. To the solution was added a solution of 1c (1.45 g, 4.07 mmol) in CH2Cl2 (10 mL). The
mixture was warmed to room temperature and stirred overnight. The resulting solution was
filtered and the filtrate was concentrated to about half of the volume. Diethyl ether (30 mL)
was added. Yellowish precipitates were formed. The precipitates were collected by filtration,
washed with diethyl ether (15 mL×2), and dried in vacuo to give a yellowish powder of 2e
(2.58 g, 92%), m.p. 237ꢀ238 °C. 1H NMR: δ 0.81 (d, J = 6.6 Hz, 12H), 3.15ꢀ3.34 (m, 2H), 5.81
(s, 2H), 6.33ꢀ6.39 (m, 2H), 6.65 (t, J = 7.5 Hz, 1H), 6.84ꢀ6.91 (m, 3H), 7.07 (t, J = 7.6 Hz, 1H),
7.22ꢀ7.51 (m, 13H), 7.63ꢀ7.70 (m, 4H), 10.52 (s, 1H). 13C NMR: δ 23.6, 28.8, 53.4, 117.3,
120.2, 122.7, 123.4, 124.0, 127.3, 128.5, 128.7, 129.3 (d, J = 7.8 Hz), 130.0, 132.0, 132.3,
132.4, 132.7, 137.4, 148.4. 31P NMR: δ 6.91. Anal. Calcd. for C40H42BrN4Pꢁ0.7CH2Cl2: C,
65.26; H, 5.84; N, 7.48%. Found: C, 65.28; H, 5.99; N, 7.68%. (The sample for elemental
analysis was recrystallized from CH2Cl2).
Synthesis of [o-(n-PrNHP(Ph2)N)C6H4N(CH)2N(Bn)CH]+Br− (2f). nꢀPrNHPPh2 (0.50 g,
2.06 mmol) was dissolved in CH2Cl2 (10 mL) and cooled to 0 °C. To the solution was added a
solution of 1c (0.68 g, 1.91 mmol) in CH2Cl2 (10 mL). The mixture was warmed to room
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temperature and stirred overnight. The resulting solution was filtered and the filtrate was
concentrated to about half of the volume. Diethyl ether (30 mL) was added. Yellowish
precipitates were formed. The precipitates were collected by filtration, washed with diethyl
ether (15 mL×2), and dried in vacuo to give a yellowish powder of 2f⋅0.14CH2Cl2⋅0.83Et2O
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(1.04 g, 84%), m.p. 96ꢀ97 °C. H NMR: δ 0.83 (t, J = 7.2 Hz, 3H), 1.20 (t, J = 7.2 Hz , 5.2H,
Et2O), 1.48ꢀ1.60 (m, 2H), 2.78ꢀ2.88 (m, 2H), 3.48 (q, J = 7.2 Hz , 3.3H, Et2O), 3.84 (b, 1H),
5.29 (s, 0.28H, CH2Cl2), 5.89 (s, 2H), 6.72 (t, J = 7.2 Hz, 1H), 6.82 (d, J = 8.1 Hz, 1H),
7.01ꢀ7.07 (m, 1H), 7.29ꢀ7.36 (m, 4H), 7.37ꢀ7.44 (m, 4H), 7.46ꢀ7.51 (m, 4H), 7.54ꢀ7.56 (m, 2H),
7.71ꢀ7.78 (m, 4H), 10.36 (s, 1H). 13C NMR: δ 11.5, 15.4, 25.0 (d, J = 7.4 Hz), 43.2, 53.5, 65.9,
120.7, 123.1, 123.3, 123.6, 125.0, 128.9, 129.1, 129.3, 129.4, 130.6, 132.0, 132.1, 133.7, 137.4.
31P NMR: δ 7.96. Anal. Calcd. for C31H32BrN4P: C, 65.15; H, 5.64; N, 9.80%. Found: C, 65.26;
H, 5.84; N, 9.73%. (The sample for elemental analysis was recrystallized from CH2Cl2).
Synthesis of [o-(t-BuNHP(Ph2)N)C6H4N(CH)2N(Bn)CH]+Br− (2g) tꢀBuNHPPh2 (1.80 g,
7.00 mmol) was dissolved in CH2Cl2 (10 mL) and cooled to 0 °C. To the solution was added a
solution of 1c (2.30 g, 6.46 mmol) in CH2Cl2 (10 mL). The resulting mixture was warmed to
room temperature and stirred overnight. The solution was filtered and the filtrate was
concentrated to about half of the volume. Diethyl ether (30 mL) was added. Yellowish
precipitates were formed. The precipitates were collected by filtration, washed with diethyl
ether (15 mL×2), and dried in vacuo to give a yellowish powder of 2gꢁ0.13CH2Cl2ꢁ0.2Et2O
1
(3.70 g, 93%), m.p. 217ꢀ218 °C. H NMR: δ 1.13 (s, 9H), 1.20 (t, J = 6.9 Hz, 1.26H, Et2O),
3.14 (d, J = 8.4 Hz, 1H), 3.48 (q, J = 6.9 Hz, 0.81H, Et2O), 5.29 (s, 0.25H, CH2Cl2), 5.96 (s,
2H), 6.72ꢀ6.77 (m, 1H), 6.83 (d, J = 8.4 Hz, 1H), 7.05ꢀ7.10 (m, 1H), 7.30ꢀ7.48 (m, 10H),
7.51ꢀ7.55 (m, 2H), 7.65 (t, J = 1.8 Hz, 1H), 7.69ꢀ7.77 (m, 4H), 7.80 (s, 1H), 10.07 (s, 1H). 13C
NMR: δ 32.0, 53.6, 65.9, 117.7, 121.1, 123.5 (d, J = 14 Hz), 124.4, 125.7, 128.9, 129.1, 129.3,
31
129.4, 130.6, 131.6, 131.7, 131.9 (d, J = 2 Hz), 133.7, 136.7. P NMR: δ −1.19. Anal. Calcd.
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for C32H34BrN4Pꢁ0.1CH2Cl2: C, 64.91; H, 5.80; N, 9.43%. Found: C, 64.66; H, 5.93; N, 9.57%.
(The sample for elemental analysis was recrystallized from CH2Cl2).
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suspension of 2a (0.51 g, 0.86 mmol) in THF (15 mL) was added dropwise nꢀBuLi (0.70 mL, a
2.5M of solution in hexanes, 1.75 mmol) at about −80 °C. The mixture was warmed to room
temperature and stirred for 3 h. The resultant solution was transferred to a stirred suspension of
(DME)NiCl2 (0.19 g, 0.86 mmol) in THF (10 mL) at about −80 °C. The mixture was stirred for
20 h at room temperature. Solvent was removed in vacuo. The residual solid was dissolved in
CH2Cl2 and then filtered. The filtrate was concentrated to form pink crystals of 3aꢁ0.09CH2Cl2
(0.39 g, 69%), m.p. 227ꢀ228 °C. 1H NMR: δ 2.13 (s, 3H), 4.20 (s, 3H), 5.30 (s, 0.17H, CH2Cl2),
6.35 (d, J = 7.8 Hz, 1H), 6.60ꢀ6.78 (m, 6H), 6.99 (s, 1H), 7.21 (d, J = 7.8 Hz, 1H), 7.31 (s, 1H),
7.48ꢀ7.62 (m, 6H), 8.04 (dd, J = 8.1, 11.7 Hz, 4H). 13C NMR: δ 20.9, 43.8, 118.2, 119.2, 119.6,
119.8, 120.0, 125.5, 126.6, 126.8, 128.7, 129.0, 129.2, 130.1, 132.3, 132.5, 132.9 (d, J = 2.8
Hz), 153.2. 31P NMR: δ 46.77. Anal.Calcd. for C29H26IN4PNiꢁ0.4CH2Cl2: C, 51.85; H, 3.97; N,
8.23%. Found: C, 51.82; H, 4.05; N, 8.43%. (The sample for elemental analysis was
recrystallized from CH2Cl2).
Synthesis of [Ni(I){o-(4-MeC6H4NP(Ph2)=N)C6H4N(CH)2N(i-Pr)C}] (3b). To a stirred
suspension of 2b (0.46 g, 0.74 mmol) in THF (10 mL) was added nꢀBuLi (0.60 mL, a 2.5 M of
solution in hexanes, 1.5 mmol) at about −80 °C. The mixture was warmed to room temperature
and stirred for 4 h. The resultant solution was transferred to a stirred suspension of
(DME)NiCl2 (0.16 g, 0.74 mmol) in THF (10 mL) at about −80 °C. The mixture was allowed
to warm to room temperature and stirred overnight. The precipitates were collected by filtration
and then dissolved in CH2Cl2. The solution was filtered and the filtrate was concentrated to
generate purple crystals of 3bꢁ0.09CH2Cl2 (0.41 g, 81%), m.p. 196ꢀ198 °C. 1H NMR: δ 1.61 (d,
J = 6.6 Hz, 6H), 2.12 (s, 3H), 5.30 (s, 0.19H, CH2Cl2), 5.91ꢀ6.04 (m, 1H), 6.32 (d, J = 7.8 Hz,
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1H), 6.57ꢀ6.78 (m, 6H), 7.09 (s, 1H), 7.20 (d, J = 7.8 Hz, 1H), 7.35 (s, 1H), 7.46ꢀ7.62 (m, 6H),
8.03ꢀ8.10 (m, 4H). 13C NMR: δ 20.9, 23.7, 54.6, 118.2, 119.2, 120.1 (d, J = 10 Hz), 120.2 (d, J
= 4.1 Hz), 125.4, 126.5, 126.7, 128.7, 129.0, 129.1, 129.9, 130.1, 131.3, 132.3, 132.5, 132.8 (d,
J = 2.6 Hz), 136.0, 141.8, 152.3. 31P NMR: δ 46.14. Anal. Calcd. for C31H30IN4PNiꢁ0.3CH2Cl2:
C, 53.66; H, 4.40; N, 8.00%. Found: C, 53.79; H, 4.58; N, 8.05%. (The sample for elemental
analysis was recrystallized from CH2Cl2).
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Synthesis of [Ni(Br){o-(4-MeC6H4NP(Ph2)=N)C6H4N(CH)2N(Bn)C}] (3c). To a stirred
suspension of 2cꢁ0.33CH2Cl2 (0.662 g, 1.00 mmol) in THF (10 mL) was added nꢀBuLi (0.80
mL, a 2.5M solution in hexanes, 2.00 mmol) at about −80 °C. The mixture was warmed to
room temperature and stirred for 4 h. The resultant solution was added dropwise to a stirred
suspension of (DME)NiCl2 (0.22 g, 1.00 mmol) in THF (10 mL) at about −80 °C. The mixture
was warmed to room temperature and stirred overnight. Solvent was removed in vacuo, and the
residue was dissolved in CH2Cl2. The resultant solution was filtered. The filtrate was
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concentrated to give brown crystals of 3cꢁ0.21CH2Cl2 (0.56 g, 80%), m.p. 235ꢀ236 °C. H
NMR: δ 2.10 (s, 3H), 5.29 (s, 0.42H, CH2Cl2), 5.95 (s, 2H), 6.32 (d, J = 7.5 Hz, 1H), 6.58ꢀ6.80
(m, 6H), 6.82ꢀ6.85 (m, 1H), 7.20 (d, J = 7.8 Hz, 1H), 7.27ꢀ7.76 (m, 12H), 8.03ꢀ8.14 (m, 4H).
13C NMR: δ 20.8, 55.1, 56.2, 118.1, 118.2, 118.7, 118.9, 119.0, 119.2, 119.8 (d, J = 9.7 Hz),
124.1, 124.2, 125.2, 125.4, 125.5, 125.9 (d, J = 11.5 Hz), 128.2, 128.8, 128.87, 128.9, 129.0,
129.2, 129.8 (d, J = 9.9 Hz), 131.1, 132.4, 132.6, 132.9 (d, J = 2.3 Hz), 135.8, 137.1, 140.4,
148.8, 150.8. 31P NMR: δ 46.26. Anal. Calcd. for C35H30BrN4PNiꢁ0.25CH2Cl2: C, 60.70; H,
4.41; N, 8.03%. Found: C, 60.46; H, 4.46; N, 8.05%.
Synthesis of [Ni(Br){o-(4-MeOC6H4NP(Ph2)=N)C6H4N(CH)2N(Bn)C}] (3d). To a
stirred suspension of 2dꢁ0.2Et2O (0.62 g, 0.95 mmol) in THF (15 mL) was added nꢀBuLi (0.76
mL, a 2.5M solution in hexanes, 1.90 mmol) at about −80 °C. The mixture was warmed to
room temperature and stirred for 3 h. The resultant solution was added dropwise to a stirred
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suspension of (DME)NiCl2 (0.21g, 0.95 mmol) in THF (10 mL) at about −80 °C. The mixture
was warmed to room temperature and stirred overnight. Solvent was removed in vacuo, and the
residue was dissolved in CH2Cl2. The resultant solution was filtered, and the filtrate was
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concentrated to give yellow crystals of 3dꢁ0.12CH2Cl2 (0.52 g, 78%), m.p. 174ꢀ176 °C. H
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NMR: δ 3.63 (s, 3H), 5.30 (s, 0.23H, CH2Cl2), 5.94 (s, 2H), 6.31 (d, J = 7.8 Hz, 1H), 6.45ꢀ6.77
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(m, 6H), 6.83 (s, 1H), 7.16ꢀ7.45 (m, 5H), 7.47ꢀ7.74 (m, 8H), 7.99ꢀ8.13 (m, 4H). C NMR: δ
55.4, 56.1, 113.7, 113.8, 118.2, 118.7, 118.9, 119.1, 119.3, 119.7, 119.9, 124.2, 125.6, 127.2,
127.4, 128.2, 128.8, 128.9, 129.00, 129.2, 132.4, 132.5, 132.9. 31P NMR: δ 46.75. Anal. Calcd.
for C35H30BrN4PONiꢁ0.4CH2Cl2: C, 58.55; H, 4.28; N, 7.72. Found: C, 58.61; H, 4.32; N, 7.75.
(The sample for elemental analysis was recrystallized from CH2Cl2).
Synthesis of [Ni(Br){o-(2,6-i-Pr2C6H3NP(Ph2)=N)C6H4N(CH)2N(Bn)C}] (3e). To a
stirred suspension of 2eꢁ0.7CH2Cl2 (0.69 g, 0.92 mmol) in THF (15 mL) was added nꢀBuLi
(0.74 mL, a 2.5M solution in hexanes, 1.85 mmol) at about −80 °C. The mixture was warmed
to room temperature and stirred for 3 h. The resultant solution was added dropwise to a stirred
suspension of (DME)NiCl2 (0.20 g, 0.92 mmol) in THF (10 mL) at about −80 °C. The mixture
was warmed to room temperature and stirred overnight. Solvent was removed in vacuo, and the
residue was dissolved in CH2Cl2. The resultant solution was filtered, and the filtrate was
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concentrated to give brown crystals of 3e (0.52 g, 76%). m.p. 264ꢀ266 °C. H NMR: δ
0.32ꢀ0.37 (m, 6H), 1.39ꢀ1.42 (m, 6H), 4.11ꢀ4.32 (m, 2H), 5.88 (s, 2H), 6.08 (d, J = 8.1 Hz, 1H),
6.47ꢀ6.52 (m, 1H), 6.64ꢀ6.70 (m, 1H), 6.77ꢀ6.79 (m, 1H), 6.83ꢀ6.96 (m, 3H), 7.24ꢀ7.46 (m,
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11H), 7.81ꢀ7.89 (m, 4H). C NMR: δ 22.9, 25.4, 29.1, 54.6, 55.9, 118.3, 118.8, 118.9, 119.5,
121.4 (d, J = 10.7 Hz), 122.9, 123.7, 123.9, 124.0, 125.2, 128.1, 128.5, 128.6, 128.8, 131.6,
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131.7, 132.2, 147.9. P NMR: δ 47.94. Anal. Calcd. for C40H40BrN4PNiꢁ0.4CH2Cl2: C, 62.18;
H, 5.27; N, 7.18%. Found: C, 62.16; H, 5.25; N, 7.37%. (The sample for elemental analysis
was recrystallized from CH2Cl2).
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Synthesis of [Ni(Br){o-(n-PrNP(Ph2)=N)C6H4N(CH)2N(Bn)C}] (3f). To a stirred
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suspension of 2f (0.69 g, 1.20 mmol) in THF (15 mL) was added nꢀBuLi (0.96mL, a 2.5M
solution in hexanes, 2.40 mmol) at about −80 °C. The mixture was warmed to room
temperature and stirred for 3 h. The resultant solution was added dropwise to a stirred
suspension of (DME)NiCl2 (0.27 g, 1.20 mmol) in THF (10 mL) at about −80 °C. The mixture
was warmed to room temperature and stirred overnight. Solvent was removed in vacuo, and the
residue was dissolved in CH2Cl2. The resultant solution was filtered, and the filtrate was
concentrated to give green powder of 3fꢁ1.45CH2Cl2 (0.65 g, 72%), m.p. 251ꢀ252 °C. This
complex is paramagnetic. IR: ν (cm−1) 3270vs, 2960s, 2930m, 2870m, 1620w, 1610w, 1590w,
1490s, 1460m, 1440s, 1260s, 1230m, 1100vs, 1030s, 995s, 819s, 743s, 723s, 691s, 629m. Anal.
Calcd. for C31H30BrN4PNiꢁ1.45CH2Cl2: C, 51.88; H, 4.41; N, 7.46%. Found: C, 51.79; H, 4.67;
N, 7.54%. (The sample for elemental analysis was recrystallized from CH2Cl2).
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Synthesis of [Ni(Br){o-(t-BuNP(Ph2)=N)C6H4N(CH)2N(Bn)C}] (3g). To a stirred
suspension of 2gꢁ0.1CH2Cl2 (0.58 g, 0.98 mmol) in THF (15 mL) was added nꢀBuLi (0.80 mL,
a 2.5M solution in hexanes, 2 mmol) at about −80 °C. The mixture was warmed to room
temperature and stirred for 3 h. The resultant solution was added dropwise to a stirred
suspension of (DME)NiCl2 (0.22 g, 1.00 mmol) in THF (10 mL) at about −80 °C. The mixture
was warmed to room temperature and stirred overnight. Solvent was removed in vacuo, and the
residue was dissolved in CH2Cl2. The resultant solution was filtered, and the filtrate was
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concentrated to give blue crystals of 3g (0.35 g, 56%), m.p. 235ꢀ237 °C. H NMR: δ 1.03 (d, J
= 3.3 Hz, 9H), 5.89 (s, 1H), 5.92 (s, 1H), 6.09ꢀ6.14 (m, 1H), 6.52ꢀ6.62 (m, 2H), 6.86 (d, J = 9.6
Hz, 1H), 7.09ꢀ7.19 (m, 2H), 7.37ꢀ7.65 (m, 9H), 7.93 (d, J = 7.2 Hz, 1H), 8.00 (d, J = 7.5 Hz,
1H), 8.21ꢀ8.31 (m, 4H). 13C NMR: δ 33.1 (d, J = 8.7 Hz), 33.4 (d, J = 8.7 Hz), 51.3, 51.6, 54.9,
55.9, 117.0 (d, J = 4 Hz), 118.4, 118.7, 118.8, 119.0, 119.4, 119.5, 119.6, 124.2, 124.5, 125.3,
125.5, 128.1 (d, J = 5.7 Hz), 128.7, 128.9, 129.0, 132.1, 132.6, 132.8, 149.0. 31P NMR: δ 42.44.
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Anal. Calcd. for C32H32BrN4PNiꢁ0.1CH2Cl2: C, 59.25; H, 4.99; N, 8.61%. Found: C, 59.19; H,
5.28; N, 8.79%. (The sample for elemental analysis was recrystallized from CH2Cl2).
General Procedures for the Cross-Coupling Reactions. A Schlenk tube was charged with
nickel complex (the amount needed), aryl halide (0.5 mmol) and THF (1.5 mL). To the solution
was added dropwise a solution of ArMgBr (1.5 mL, 0.5 M in THF, 0.75 mmol) at 25 °C and
stirred for 24 h. The reaction was quenched with water and the mixture was extracted with
diethyl ether (3 × 5 mL). The combined organic phases were dried over Na2SO4, concentrated
by rotary evaporation and purified by column chromatography on silica gel (eluent: a mixture
of petroleum ether and ethyl acetate).
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Spectral data of the cross-coupling products. 4-(N,N-Dimethylamino)-2’,5’-dimethyl
biphenyl.26 1H NMR: δ 2.26 (s, 3H), 2.32 (s, 3H), 2.96 (s, 6H), 6.76 (d, J = 8.7 Hz, 2H), 7.00 (d,
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J = 7.5 Hz , 1H), 7.05 (s, 1H), 7.12 (d, J = 7.5 Hz, 1H), 7.21 (d, J = 8.7 Hz, 2H). C NMR: δ
20.3, 21.1, 29.8, 40.7, 112.2, 127.3, 130.0, 130.3, 130.8, 132.4, 135.2, 141.9, 149.5.
4'-Methoxy-2,5-dimethylbiphenyl.27 1H NMR: δ 2.22 (s, 3H), 2.32 (s, 3H), 3.81 (s, 3H), 6.92
(d, J = 8.7 Hz, 2H), 7.04 (s, 2H), 7.12ꢀ7.16 (m, 1H), 7.23 (d, J = 8.7 Hz, 2H). 13C NMR: δ 20.1,
21.0, 29.8, 55.3, 113.6, 127.8, 130.3, 130.8, 132.4, 134.6, 135.2, 141.5, 158.6.
4'-Methy-2,5-dimethylbiphenyl.28 1H NMR: δ 2.22 (s, 3H), 2.32 (s, 3H), 2.38 (s, 3H), 7.04 (s,
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2H), 7.12ꢀ7.14 (m, 1H), 7.17ꢀ7.22 (m, 4H). C NMR: δ 20.1, 21.0, 21.3, 126.9, 127.9, 128.9,
129.2, 129.6, 130.4, 130.7, 132.3, 135.2, 136.4, 139.3, 141.9.
3,4-Dimethoxy-4’-methylbiphenyl.29 1H NMR: δ 2.37 (s, 3H), 3.89 (s, 3H), 3.92 (s, 3H), 6.89
(d, J = 8.1 Hz, 1H), 7.06ꢀ7.13 (m, 2H), 7.21 (d, J = 7.8 Hz, 2H), 7.44 (d, J = 8.1 Hz, 2H). 13C
NMR: δ 21.3, 56.0, 56.1，110.5, 111.6, 119.3, 126.8, 129.6, 134.4, 136.7, 138.3, 148.5, 149.2.
3,4-Dimethoxy-4’-methoxybiphenyl.29 1H NMR: δ 3.85 (s, 3H), 3.92 (s, 3H), 3.94 (s, 3H),
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6.91ꢀ6.97 (m, 3H), 7.06ꢀ7.11 (m, 2H), 7.46ꢀ7.50 (m, 2H). C NMR: δ 29.8, 55.5, 56.0, 56.1,
110.4, 111.7, 114.3, 119.1, 128.0, 133.8, 134.1, 148.3, 149.3, 159.0.
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3,4-Dimethoxy-4’-N,N-dimethylaminobiphenyl. Yellowish crystalline solid, m.p. 138ꢀ140 ºС.
1H NMR: δ 2.98 (s, 6H), 3.90 (s, 3H), 3.94 (s, 3H), 6.80 (d, J = 8.7 Hz, 2H), 6.91 (d, J = 8.1 Hz,
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1H), 7.07ꢀ7.11 (m, 2H), 7.46 (d, J = 9 Hz, 2H). C NMR: δ 40.7, 56.0, 56.1, 110.1, 111.8,
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113.0, 118.6, 127.5, 129.5, 133.3, 134.6, 147.9, 149.3, 149.8. HRꢀMS (EI): m/z 257.1413 [M]+,
calcd for C16H19NO2 257.1416.
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4-(4-Methoxyphenyl)benzyl alcohol.30 1H NMR: δ 1.75 (s, 1H), 3.85 (s, 3H), 4.72 (s, 2H),
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6.98 (d, J = 8.7 Hz, 2H), 7.41 (d, J = 8.1 Hz, 2H), 7.51ꢀ7.55 (m, 4H). C NMR: δ 55.5, 65.3,
114.4, 127.0, 127.6, 128.2, 133.5, 139.4, 140.4, 159.4.
4-(4-Methylphenyl)benzyl alcohol.31 1H NMR: δ 1.74 (s, 1H), 2.39 (s, 3H), 4.73 (d, J = 3.6
Hz , 2H), 7.25 (d, J = 7.8 Hz, 2H), 7.42 (d, J = 8.1 Hz, 2H), 7.49 (d, J = 7.8 Hz, 2H), 7.58 (d, J
= 8.1 Hz, 2H). 13C NMR: δ 21.2, 65.3, 127.1, 127.2, 127.6, 129.6, 137.2, 138.1, 139.7, 140.7.
[4-(4-Dimethylaminophenyl)phenyl]methanol. Pale yellow microcrystals, m.p. 142ꢀ144 ºС.
1H NMR: δ 1.70 (s, 1H), 2.99 (s, 6H), 4.70 (s, 2H), 6.80 (d, J = 9 Hz, 2H), 7.39 (d, J = 8.4 Hz,
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2H), 7.50 (d, J = 8.7 Hz, 2H), 7.55 (d, J = 8.1 Hz, 2H). C NMR: δ 40.7, 65.4, 112.9, 126.6,
127.7, 127.8, 128.9, 138.7, 140.8, 150.2. HRꢀMS (EI): m/z 227.1308 [M]+, calcd for C15H17NO
227.1310.
1-(4-Methylphenyl)naphthalene.32 1H NMR: δ 2.44 (s, 3H), 7.29 (d, J = 8.1 Hz, 2H),
7.37ꢀ7.52 (m, 6H), 7.81ꢀ7.93 (m, 3H). 13C NMR: δ 21.4, 125.5, 125.8, 126.1, 126.2, 127.0,
127.6, 128.4, 129.1, 130.1, 131.9, 134.0, 137.0, 138.0, 140.4.
1-(4-Methoxyphenyl)naphthalene.33 1H NMR: δ 3.88 (s, 3H), 7.02 (d, J = 8.4 Hz, 2H),
7.39ꢀ7.53 (m, 6H), 7.81ꢀ7.94 (m, 3H). 13C NMR: δ 55.5, 113.9, 125.5, 125.8, 126.1, 126.2,
127.0, 127.5, 128.4, 131.3, 132.0, 133.3, 134.0, 140.1, 159.1.
1-(4-N,N-Dimethylaminophenyl)naphthalene.34 1H NMR: δ 3.02 (s, 6H), 6.86 (d, J = 9 Hz,
2H), 7.38ꢀ7.52 (m, 6H), 7.80 (d, J = 8.1 Hz, 1H), 7.88 (d, J = 7.8 Hz, 1H), 8.02 (d, J = 8.1 Hz,
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1H). C NMR: δ 40.8, 112.4, 125.6, 125.7, 125.8, 126.5, 126.9, 127.0, 128.4, 131.0, 132.1,
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134.1, 140.6, 149.9.
4-Methylbiphenyl.35 1H NMR: δ 2.36 (s, 3H), 7.21 (d, J = 7.8 Hz, 2H), 7.29 (t, J = 7.2 Hz,
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1H), 7.39 (t, J = 7.2 Hz, 1H), 7.47 (d, J = 8.1 Hz , 2H), 7.55 (d, J = 7.2 Hz, 2H). C NMR: δ
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4-Methoxy-4'-methylbiphenyl.35 1H NMR: δ 2.38 (s, 3H), 3.86 (s, 3H), 6.96 (d, J = 8.7 Hz,
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2H), 7.22 (D, J = 7.8 Hz, 2H), 7.44 (d, J = 8.1 Hz, 2H), 7.50 (d, J = 8.7 Hz, 2H). C NMR: δ
21.1, 55.4, 114.3, 126.7, 128.0, 129.6, 133.8, 136.4, 138.1, 159.1.
1-Methoxy-2-p-tolylbenzene.35 1H NMR: δ 2.38 (s, 3H), 3.79 (s, 3H), 6.95ꢀ7.03 (m, 2H),
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7.21 (d, J = 7.8 Hz, 2H), 7.30 (d, J = 7.5 Hz, 2H), 7.42 (d, J = 8.1 Hz, 2H). C NMR: δ21.3,
55.7, 111.4, 120.9, 128.5, 128.9, 129.5, 130.9, 135.8, 136.7, 156.7.
2-p-Tolylpyridine.35 1H NMR: δ 2.39 (s, 3H), 7.14ꢀ7.20 (m, 1H), 7.25 (d, J = 8.1 Hz, 2H),
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7.65ꢀ7.69 (m, 2H), 7.88 (d, J = 8.4 Hz, 2H), 8.66 (dt, J = 1.2, 4.8 Hz, 1H). C NMR: δ 21.3,
115.5, 120.3, 121.9, 126.9, 129.6, 130.0, 136.8, 139.0, 149.7, 157.6.
N,N-Diethyl-4'-methylbiphenyl-4-carboxamide.35 1H NMR: δ 1.13 (b, 3H), 1.24 (b, 3H), 2.38
(s, 3H), 3.30 (b, 2H), 3.54 (b, 2H), 7.24 (d, J = 8.1 Hz, 2H), 7.42 (d, J = 8.4 Hz, 2H), 7.48 (d, J
= 8.1 Hz, 2H), 7.58 (d, J = 8.4 Hz, 2H). 13C NMR: δ 12.9, 14.1, 21.0, 39.3, 43.3, 126.8, 126.9,
129.5, 135.8, 137.4, 141.9, 171.1.
4'-Methylbiphenyl-4-carbonitrile.35 1H NMR: δ 2.44 (s, 3H), 7.29 (d, J = 7.8 Hz, 2H), 7.45
(d, J = 8.4 Hz, 2H), 7.69 (d, J = 8.1 Hz, 2H), 7.73 (d, J = 8.4 Hz, 2H). 13C NMR: δ 21.8, 128.7,
129.2, 130.3, 131.5, 133.5, 134.7, 136.4, 138.7, 143.7, 195.4.
4'-Methylbiphenyl-2-carbonitrile.17c 1H NMR: δ 2.36 (s, 3H), 7.18 (d, J = 7.8 Hz, 2H),
7.29ꢀ7.37 (m, 3H), 7.39ꢀ7.43 (m, 1H), 7.53 (d, J = 6.9 Hz, 2H). 13C NMR: δ 21.5, 126.9, 127.9,
129.2, 129.4, 129.9, 130.1, 130.3, 134.9, 139.8, 141.4, 175.6.
2'-Methylbiphenyl-4-carbonitrile.36 1H NMR: δ 2.12 (s, 3H), 7.17 (d, J = 7.8 Hz, 1H),
7.22ꢀ7.27 (m, 2H), 7.31ꢀ7.35 (m, 3H), 7.62 (d, J = 8.1 Hz, 2H). 13C NMR: δ 19.8, 126.1, 127.5,
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128.7, 129.1, 129.5, 130.6, 134.5, 136.8, 137.2, 140.4, 177.7.
2'-Methylbiphenyl-2-carbonitrile.37 1H NMR: δ 2.31 (s, 3H), 7.15ꢀ7.41 (m, 8H). 13C NMR: δ
20.6, 125.8, 127.0, 129.0, 129.6, 130.3, 130.5, 130.6, 131.2, 139.9, 177.7.
4'-Methoxy-2-methylbiphenyl.35 1H NMR: δ 2.27 (s, 3H), 3.84 (s, 3H), 6.94 (d, J = 8.7 Hz,
2H), 7.16ꢀ7.26 (m, 6H). 13C NMR: δ 20.7, 55.4, 113.6, 125.9, 127.1, 130.0, 130.4, 134.5, 135.6,
141.7, 158.7.
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2-o-Tolylpyridine.38 1H NMR: δ 2.35 (s, 3H), 7.10ꢀ7.18 (m, 1H), 7.21ꢀ7.27 (m, 3H),
7.32ꢀ7.39 (m, 2H), 7.61ꢀ7.68 (m, 1H), 8.66 (d, J = 3.9 Hz, 1H). 13C NMR: δ 20.2, 121.5, 123.9,
125.7, 128.1, 129.5, 130.6, 135.6, 136.0, 140.3, 149.0, 159.9.
4-Methoxybiphenyl.39 1H NMR: δ 3.85 (s, 3H), 6.98 (d, J = 9 Hz, 2H), 7.27ꢀ7.33 (m, 1H),
7.42 (t, J = 7.5 Hz, 2H), 7.51ꢀ7.57 (m, 4H). 13C NMR: δ 55.4, 114.3, 126.8, 126.8, 128.2, 128.8,
133.8, 140.9, 159.2.
2-(p-Methoxyphenyl)pyridine.40 1H NMR: δ 3.86 (s, 3H), 7.00 (d, J = 9 Hz, 2H), 7.14ꢀ7.19
(m, 1H), 7.64ꢀ7.73 (m, 2H), 7.95 (d, J = 9 Hz, 2H), 8.65 (d, J = 4.2 Hz, 1H). 13C NMR: δ 55.5,
114.2, 119.9, 121.5, 128.3, 132.2, 136.8, 149.7, 157.3, 160.6.
N,N-Diethyl-4'-methoxybiphenyl-4-carboxamide.41 1H NMR: δ 1.21 (b, 6H), 3.35 (b, 2H),
3.54 (b, 2H), 3.85 (s, 3H), 6.98 (d, J = 8.7 Hz, 2H), 7.42 (d, J = 8.1 Hz, 2H), 7.51ꢀ7.58 (m, 4H).
13C NMR: δ 13.0, 14.3, 39.3, 43.4, 55.4, 114.4, 126.6, 126.9, 128.2, 132.9, 135.5, 141.7, 159.5,
171.3.
4-(Dimethylamino)biphenyl.35 1H NMR: δ 2.99 (s, 6H), 6.80 (d, J = 8.7 Hz, 2H), 7.24ꢀ7.27
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(m, 1H), 7.39 (t, J = 7.8 Hz, 2H), 7.49ꢀ7.57 (m, 4H). C NMR: δ 40.9, 113.1, 113.9, 114.0,
126.2, 126.46, 126.54, 127.8, 127.9, 128.8.
2'-Methyl-N,N-dimethylbiphenyl-4-amine.42 1H NMR: δ 2.30 (s, 3H), 2.95 (s, 6H), 6.76 (d, J
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= 8.4 Hz, 2H), 7.17ꢀ7.24 (m, 6H). C NMR: δ 20.8, 40.7, 112.2, 125.8, 126.6, 130.0, 130.4,
135.6, 142.2, 149.5.
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4'-Methyl-N,N-dimethylbiphenyl-4-amine.43 1H NMR: δ 2.37 (s, 3H), 2.98 (s, 6H), 6.78 (d, J
= 8.7 Hz, 2H), 7.21 (t, J = 7.8 Hz, 2H), 7.47 (t, J = 8.4 Hz, 4H). 13C NMR: δ 21.1, 40.7, 113.0,
126.3, 127.6, 129.5, 135.7, 138.5, 149.9.
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2'-Methoxy-N,N-dimethylbiphenyl-4-amine.44 1H NMR: δ 2.96 (s, 6H), 3.78 (s, 3H), 6.78 (d,
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J = 8.7 Hz, 2H), 6.92ꢀ7.01 (m, 2H), 7.19ꢀ7.32 (m, 2H), 7.44 (d, J = 8.7 Hz, 2H). C NMR: δ
40.7, 55.7, 111.4, 112.3, 120.9, 126.7, 127.7, 130.3, 130.6, 131.0, 149.7, 156.7.
4'-Methoxy-N,N-dimethylbiphenyl-4-amine.35 1H NMR: δ 2.98 (s, 6H), 3.83 (s, 3H), 6.80 (d,
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J = 8.4 Hz, 2H), 6.94 (d, J = 8.1 Hz, 2H), 7.43ꢀ7.49 (m, 4H). C NMR: δ 40.9, 55.5, 113.2,
114.3, 127.5, 134.1, 149.7, 158.4.
2-(p-N,N-Dimethylaminophenyl)pyridine.45 1H NMR: δ 3.01 (s, 6H), 6.79 (d, J = 8.7 Hz, 2H),
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7.05ꢀ7.13 (m, 1H), 7.61ꢀ7.69 (m, 2H), 7.91 (d, J = 8.7 Hz, 2H), 8.61 (d, J = 4.5 Hz, 1H). C
NMR: δ 40.5, 112.4, 119.3, 120.7, 127.8, 136.6, 149.5, 151.2, 157.7.
1,4-Di(p-methylphenyl)benzene.15f 1H NMR: δ 2.40 (s, 6H), 7.26 (d, J = 7.2 Hz, 4H), 7.54 (d,
J = 8.1 Hz, 4H), 7.64 (s, 4H). 13C NMR: δ 21.3, 127.0, 127.4, 129.7, 137.2, 138.1, 139.9.
1,4-Di(p-methoxyphenyl)benzene.46 1H NMR: δ 3.86 (s, 6H), 6.99 (d, J = 8.7 Hz, 4H), 7.57
(d, J = 8.7 Hz, 4H), 7.61 (s, 4H). 13C NMR: δ 55.5, 114.4, 127.2, 128.2, 133.5, 139.3, 159.3.
1,4-Di(N,N-dimethylaminophenyl)benzene.47 1H NMR: δ 3.00 (s, 12H), 6.82 (d, J = 8.7 Hz,
4H), 7.54 (d, J = 9 Hz, 4H), 7.59 (s, 4H). 13C NMR: δ 40.8, 113.1, 126.7, 127.7, 139.0, 150.0.
1,4-Di(o-methylphenyl)benzene.48 1H NMR: δ 2.33 (s, 6H), 7.21ꢀ7.31 (m, 8H), 7.36 (s, 4H).
13C NMR: δ 20.7, 125.9, 127.4, 129.0, 130.0, 130.5, 135.6, 140.5, 141.8.
1,2-Di(p-methylphenyl)benzene.49 1H NMR: δ 2.31 (s, 6H), 7.03 (s, 8H), 7.38 (s, 4H). C
13
NMR: δ 21.3, 127.4, 128.8, 129.8, 130.8, 136.1, 138.9, 140.6.
1,2-Di(N,N-dimethylaminophenyl)benzene.47 1H NMR: δ 2.91 (s, 12H), 6.62 (d, J = 8.7 Hz,
4H), 7.07 (d, J = 7.8 Hz, 4H), 7.26ꢀ7.41 (m, 4H). 13C NMR: δ 40.7, 112.3, 126.7, 130.4, 130.7,
140.5, 149.1.
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Acknowledgments
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This research was supported by the National Basic Research Program of China (Grant No.
2009CB825300) and the National Natural Science Foundation of China (Grant No. 21172208).
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Supporting Information
Synthetic routes of the ligand precursors and nickel complexes. Crystal structure determination
details and crystal data of complex 3e. Copies of H and 13C NMR spectra of the
1
crossꢀcoupling products. This material is available free of charge via the Internet at
http://pubs.acs.org.
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