Synthesis and characterization of novel organonickel and organocobalt complexes via carbonechlorine bond activation

Article abstract of DOI:10.1016/j.jorganchem.2013.06.033

The ortho-metalated nickel(II) complexes 3, 4, 7 and 8 were obtained by the reaction of ortho-halogeno aromatic bis-Schiff bases 1, 2, 5 and 6 with the stoichiometric amount of Ni(PM-3)4. The combination of 5 and 6 with two equivalents of Ni(PM-3)4 resulted in oxidative addition of the double CeCl bonds to afford ortho-bis-chelated nickel(II) complexes 9 and 10. The reaction of 6 with Co(PM-3)4 gave rise to dinuclear ortho-metalated cobalt(II) complex 12 through CeCl bond activation while the reaction of 5 with Co(PM-3)4 delivered bis-chelated cobalt(I) complex 11 through both CeCl and CeH bond activation. The structures of complexes 3, 4, 8, 9, 11 and 12 were determined by X-ray single crystal diffraction. The catalytic activity of bis-chelated cobalt(I) complex 11 as catalyst for C,C-coupling reaction was explored.

Full text of DOI:10.1016/j.jorganchem.2013.06.033

Journal of Organometallic Chemistry 743 (2013) 114e122
Contents lists available at SciVerse ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis and characterization of novel organonickel and
organocobalt complexes via carbonechlorine bond activation
Junye Li, Xiaoyan Li, Hongjian Sun*
School of Chemistry and Chemical Engineering, Shandong University, 250100 Jinan, People’s Republic of China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 24 April 2013
Received in revised form
The ortho-metalated nickel(II) complexes 3, 4, 7 and 8 were obtained by the reaction of ortho-halogeno
aromatic bis-Schiff bases 1, 2, 5 and 6 with the stoichiometric amount of Ni(PMe
and 6 with two equivalents of Ni(PMe resulted in oxidative addition of the double CeCl bonds to
afford ortho-bis-chelated nickel(II) complexes 9 and 10. The reaction of 6 with Co(PMe gave rise to di-
nuclear ortho-metalated cobalt(II) complex 12 through CeCl bond activation while the reaction of 5 with
Co(PMe delivered bis-chelated cobalt(I) complex 11 through both CeCl and CeH bond activation. The
3 4
) . The combination of 5
3 4
)
21 June 2013
3 4
)
Accepted 24 June 2013
3 4
)
Keywords:
structures of complexes 3, 4, 8, 9, 11 and 12 were determined by X-ray single crystal diffraction. The
catalytic activity of bis-chelated cobalt(I) complex 11 as catalyst for C,C-coupling reaction was explored.
Ó 2013 Elsevier B.V. All rights reserved.
ortho-Metalation
CeCl activation
Nickel
Cobalt
Diimine
Trimethyphosphine
1. Introduction
complexes 3, 4, 7 and 8 were obtained by oxidative addition of
aromatic CeCl bonds. The ortho-bis-chelated Ni(II) complexes 9, 10
CeCl bond activation is one of the important methods to realize
the catalytic CeCl bond functionalization [1e10]. A few strategies
have been reported for the activation of CeCl bonds of aryl chlo-
rides by transition metal complexes [11e25]. Recently, cyclo-
metalation reaction with imine as an anchoring group to activate
CeCl bond has received increasing attention. Tungsten [26], nickel
and cobalt(II) complex 12 were also isolated via double CeCl bond
activation. Interestingly, bis-chelated Co(I) complex 11 was
confirmed through both CeCl and CeH bond activation. The C,C-
coupling reaction between chlorobenzene and Grignard reagents
with complex 11 as catalyst was explored. The related reaction
mechanisms were proposed. The structures of complexes 3, 4, 8, 9,
11 and 12 were determined by X-ray single crystal diffraction. All
this work of this paper is illustrated in Scheme 1.
[27], iron [28], Platinum [29] and copper [30] complexes were re-
ported for activation of CeCl bonds. Our research interest is focused
on CeCl bond activation mediated by electron-rich cobalt, nickel
and iron complexes supported by trimethylphosphine ligands. In
the past few years, a series of ortho-chelated cobalt(II) [31], nick-
el(II) [32] and iron(II) [33] complexes were synthesized and char-
acterized through CeCl activation with imine as an anchoring
group [34]. The CeCl bonds of ortho-chlorinated benzamides were
activated by tetrakis(trimethylphosphine)nickel(0) and tetrakis(-
trimethylphosphine)cobalt(0) complexes.
As part of our continuing research work on CeCl bond activa-
tion, organic chlorides were extended from ortho-chlorinated
mono-imines in our early study to ortho-chlorinated diimine to
explore the opportunity of double CeCl bond activation through di-
ortho-metalation in this paper. The new ortho-chelated nickel(II)
2. Results and discussion
3 4
2.1. Reactions of chlorinated diimines with Ni(PMe )
3 4
Reactions of Ni(PMe ) with ortho-chlorinated aromatic com-
pounds (1 and 2) containing di-imine as anchoring groups proceed
by oxidative addition of the CeCl bond to give rise to ortho-meta-
lated nickel(II) chlorides 3 and 4 (Eq. (1)). The expected dinuclear
nickel(II) complexes (as the analog of complexes 9 and 10) formed
via double CeCl bond activation were not observed even if two
3 4
equivalents of Ni(PMe ) were added in the reaction solution. It is
suggested that the double CeCl activation was excluded owing to
the steric effect of the two adjacent imine groups. Only one of the
two imine groups can act as anchoring group.
In the infrared spectra of complexes 3 and 4, the characteristic
(C]N) bands were recorded at 1606 (3) and 1605 (4) cm .
*
Corresponding author. Tel.: þ86 531 88361350; fax: þ86 531 88564464.
E-mail address: hjsun@sdu.edu.cn (H. Sun).
ꢀ
1
n
0
022-328X/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2013.06.033

J. Li et al. / Journal of Organometallic Chemistry 743 (2013) 114e122
115
two imine groups is perpendicular to the underside of the square
pyramid. In other words, this is a symmetry plane of this molecule.
Therefore, two phosphine ligands have the same chemical envi-
ronment. This is consistent with the NMR information. The dis-
Cl
Y
Cl
N
Y
N
PMe
Cl
N
+ Ni(PMe )
Ni
Y
+
2 PMe (1)
N
Me P
ꢀ
Y
tances of NieCl are 2.2531(5) (3) and 2.2417(4) (A) in the normal
Cl
region. There is no significant difference between the coordinated
1
, 2
3, 4
ꢀ
C]N bonds (N1eC13 ¼ 1.284(2) (3) and C7eN1 ¼ 1.295(3) (4) A)
Y = H Cl
1
2
and the uncoordinated C]N bonds (N2eC14 ¼ 1.281(2) (3) and
3
4
ꢀ
C8eN2 ¼ 1.289(3) (4) A). This is in agreement with the results from
the infrared spectra. In the infrared spectra only one characteristic
Compared with the (C]N) bands (1628 and 1655 cmꢀ1) of the free
ligands 1 and 2, a substantial red shift upon coordination of the N-
donor atom of the imine group indicates a weakening of the C]N
n(C]N) bands were found. This indicates significant bond weak-
ening of the second uncoordinated C]N bond upon the coordi-
nation of the nitrogen atom of the first C]N group. Furthermore,
the N-donor of the uncoordinated C]N group becomes weaker.
Therefore, in this reaction no expected dinuclear nickel(II) com-
plexes were observed via double CeCl bond activation.
double bond after coordination to the nickel centre.
In the 1H NMR spectra, the resonances of the CH-hydrogen of
the coordinated imine groups were recorded at 10.63 (3) and 10.41
The reactions of diimines 5 and 6 with the stoichiometric amount
(4) ppm as singlet because part of the electronic cloud around of the
of Ni(PMe
and 8 via CeCl bond activation (Scheme 2). However, the reactions of
diimines 5 and 6 with 2 equivalents of Ni(PMe in THF gave rise to
3 4
) in THF afforded mono-chelated nickel(II) complexes 7
imine double bond was transferred to the nickel centre via coor-
dination and the imine hydrogen became acidic. Therefore, the
chemical shifts of these hydrogen atoms moved to the downfield. In
3 4
)
31
dinuclear nickel(II) complexes 9 and 10 with two chelate rings via
double CeCl bond activation (Scheme 2). Complexes 9 and 10 could
be also obtained through the reactions of mono-nuclear nickel(II)
the P NMR spectra, one signal at ꢀ5.5 (3) or ꢀ19.1 (4) ppm sug-
gests that the two phosphorus atoms have the same chemical
environment and are located in trans-positions.
3 4
complexes 7 and 8 with another equivalent of Ni(PMe ) . The
Complexes 3 and 4 were isolated by crystallization from pentane
ꢁ
selected IR and NMR data of complexes 7e10 are collected in Table 1.
Compared with the (C]N) bands of the free ligand 5 and 6 (1635 and
at 4 C. Both of them are stable under ambient condition and can be
handled in the air for at least 3 h. The molecular structures of
complexes 3 and 4 (Figs. 1 and 2) confirm a square-pyramidal co-
ordination of a nickel (II) centre with an imine-N atom at the apical
position. The conjugated diimine plane including two phenyl and
ꢀ1
1
649 cm ) in the IR spectra, a substantial red shift upon coordina-
tion of the N-donor atom of the imine group was also observed
owing to a weakening of the coordinated C]N group.
Cl
Y
N
PMe
N
3
Ni
Cl
Y
3, 4
Me P
3
+
Ni(PMe3)4
Cl
N
Y
Z
Y = H Cl
1
2
H
Cl 6
5 7 9
N
3
4
8 10
Y
1, 2
Cl
Z
Z
Me P
3
Cl
Cl
Z
Ni
Cl
N
N
2Ni(PMe3)4
PMe3
PMe3
+
Ni(PMe3)4
N
+
Cl
Cl
N
PMe3
N
Ni
N
Ni
5, 6
Z
Cl
PMe3
PMe3
+
2 Co(PMe3)4
Z = Cl
Z
Z = H
Z
PMe3
9, 10
7
, 8
Cl
Cl
Cl
Co
N
Me P
3
N
N
Co
N
PMe
3
Co Cl
Cl
Me P
PMe3
3
Me P
3
1
1
12
Scheme 1. Summarization of the reactions and products.

116
J. Li et al. / Journal of Organometallic Chemistry 743 (2013) 114e122
ꢁ
C7eNi1eCl (177.3(1) ) while the coordinated nitrogen and two
phosphorus atoms are in the triangular plane. The sum of three bond
angles (P1AeNi1eP2 ¼ 144.1(2), N1eNi1eP2 ¼ 103.01(8) and P1Ae
0
Ni1eN1 ¼112.34(9) ) around the nickel centre in the triangular plane
0
ꢀ
is 359.48 . The distance Ni1eCl1 (2.255(1) A) is in the normal range.
ꢀ
As expected the coordinated C]N bond (N1eC13 ¼ 1.265(4) A) is
significant longer than the uncoordinated C]N bond (N2e
ꢀ
C16 ¼ 1.250(4) A). The band of the coordinated C]N group was found
ꢀ
1
at 1613 cm while that of the uncoordinated C]N group was recor-
ꢀ
1
ded at 1647 cm in the IR spectrum of complex 8. The latter is close to
ꢀ1
that (1649 cm ) of free ligand 6. This indicates that the coordination
of the first C]N group has so less influence upon the property of the
second uncoordinated C]N that the formation of dinuclear nickel(II)
complexes 9 and 10 with two chelate rings via double CeCl bond
activation is possible. This is different from that of Eqn. (1).
Complex 9 (Fig. 4) confirms two strongly distorted tetragonal
pyramids in the crystal with the nitrogen atoms at the apical posi-
tions. In the underside of the pyramid two bond angles between the
0
trans-bonds (C1eNi1eCl1 ¼178.9(2) and P1eNi1eP2 ¼ 154.25(6) )
ꢁ
greatly deviate from 180 . The bond angles between Ni1eN1 bond
and the other four coordination bonds in the underside are in the
range of 82.6(2)e103.4(1) . The five-membered metallacycles are
formed through the coordination of the N atoms of the imine groups
Fig. 1. Molecular structure of 3 (all the hydrogen atoms were omitted for clarity).
ꢀ
ꢁ
ꢁ
Selected bond distances (A) and angles ( ): Ni1eN1 2.442(2), Ni1eP1 2.1876(5), Ni1eP2
.1920(5), Ni1eCl2 2.2531(5), Ni1eC7 1.886(2); N1eC13 1.284(2); N2eC14 1.281(2);
2
C7eNi1eN1 78.94(6), C7eNi1eP1 88.95(5), C7eNi1eP2 91.58(5), P1eNi1eN1 90.80(4).
and the ortho-metalated C atoms with a bite angle of N1eNi1e
ꢁ
ꢀ
C1 ¼ 82.6(2) . The distance of NieCl bond (Ni1eCl1 ¼ 2.273(2) A) in
All of the four complexes 7e10 were isolated as red crystals. The
molecular structures of complexes 8 and 9 (Figs. 3 and 4) were
determined by X-ray single crystal diffraction. In the molecular
structure of 8, the nickel atom attains a distorted trigonal bipyramid
with C7 and Cl1 atoms in the axial positions with the bond angle of
complex 9 is a little bit longer than those in complex 3 (Ni1e
ꢀ
ꢀ
Cl ¼ 2.2531(5) A), 4 (Ni1eCl4 ¼ 2.2417(6) A) and 8 (Ni1eCl1
ꢀ
2
.255(1) A). Complex 9 belongs to C1 point group. The phenyl ring is
in the plane of the chelate ring. Both chelate ring planes are parallel
in the molecular structure.
2.2. Reactions of chlorinated diimines with Co(PMe
3 4
)
When Co(PMe was used, instead of Ni(PMe ) , in the reac-
3
)
4
3 4
tion with diimine 5 in THF, after stirring for 12 h at room tem-
perature, the surprising bis-chelated ortho-metalated Co(I)
chloride 11 formed (Scheme 3). Complex 11 was isolated as dark
blue crystals by crystallization from diethyl ether solution
ꢁ
at ꢀ12 C. Complex 11 has a distorted trigonal bipyramid gemo-
metry with P1, P2 and N1 atoms in the equatorial plane (Fig. 5).
The three bond angles in this plane are N1eCo1eP2 ¼ 113.1(4),
ꢁ
N1eCo1eP1 ¼ 121.4(2) and P1eCo1eP2 ¼ 124.1(1) . The N2 and
C6 atoms are located in the axial positions with a bond angle C6e
ꢁ
Co1eN2 ¼ 166.1(4) . The chelate ring (Co1C6C1C7N1) and the
phenyl ring (C1eC6) are in the same plane while the chelate ring
(Co1N1C8C9N2) is nonplanar because the conjugation of the five
atoms is excluded by two aliphatic carbon atoms (C8 and C9).
Therefore, the sum of the five interior angles of the conjugated
ꢁ
chelate ring (Co1C6C1C7N1) is 540 while that of the chelate ring
0
ꢀ
(
Co1N1C8C9N2) is 529.7 . The distance of Co1eN2 (1.965(6) A) is
longer than that of Co1eN1 (1.875(7) A) due to the trans-influence
of C6 atom. N1eC7 (1.295(12) A) and N2eC10 (1.309(10) A) dis-
tances are close because both N1 and N2 atoms coordinate to the
central cobalt atom.
ꢀ
ꢀ
ꢀ
A putative mechanism of formation of complex 11 is suggested
in Scheme 3. The first step is CeCl bond activation of phenyl-A to
afford intermediate 5a. The CeCl bond cleavage is supported and
compensated by cyclometalation with the N1 and N2 as
anchoring groups. Cobalt(II) complex 5a reacts with another
equivalent of Co(PMe
3 4
) to form Co(I) complex 5b and byproduct
CoCl(PMe through comproportionation reaction. The CeH
3 3
)
Fig. 2. Molecular structure of 4 (all the hydrogen atoms were omitted for clarity).
bond activation of phenyl-B of 5b occurs to generate hydrido
intermediate 5c, a cobalt(III) species. Finally, the reductive elim-
ination between CoeH and CoeCphenyl-A bonds gave rise to
cobalt(I) complex 11. In this process the ortho-hydrogen atom of
ꢀ
ꢁ
Selected bond distances (A) and angles ( ): Ni1eN1 2.434(2), Ni1eP2 2.1935(7), Ni1e
P1 2.2000(7), Ni1eCl4 2.2417(6), Ni1eC1 1.890(2); N1eC7 1.295(3); N2eC8 1.289(3);
C1eNi1eP1 87.08(6), P1eNi1eCl4 88.76(2), P2eNi1eCl4 94.20(2), C1eNi1eP2
89.29(6), C1eNi1eN1 78.99(8), P1eNi1eN1 89.93(5).

J. Li et al. / Journal of Organometallic Chemistry 743 (2013) 114e122
117
Cl
Z
N
N
Z
Cl
5
, 6
+
Ni(PMe3)4
2
Ni(PMe
3
)
4
+
PMe3
Cl
Z
Z
Cl
Ni
N
Me P
N
PMe3
3
N
+
Ni(PMe3)
4
N
PMe3
Ni
Cl
Ni
Z
Cl
Z
Me P
3
Me P
3
7
, 8
9, 10
Z
H
5 7 9
Cl 6
8 10
Scheme 2. Reactions of Ni(PMe ) with 5 and 6.
3 4
ꢀ
1
phenyl-B transferred to the ortho-position of phenyl-A. It is
considered that the electron withdrawing ability of the ortho-
chlorine atom of phenyl-B plays an important role in this CeH
bond activation and the succedent reductive elimination. The
similar chemistry was reported with a hydridoiridium and a
hydridocobalt complex [35,36].
of CoeH bond was recorded at 1731 cm in the in situ IR spectra
1
while the hydrido resonance of CoeH bond in the H NMR spectra
in C was observed at ꢀ17.0 ppm as a broad peak. This implies
that a hydrido intermediate (e. g.: 5c) is involved in the mechanism.
Co(PMe Cl as a byproduct was also isolated and identified
6
D
6
3 3
)
through IR spectra [37]. It is regrettable that the experiments to
In order to obtain experimental evidences for the proposed re-
action mechanism, in situ IR and H NMR were carried out. A signal
isolate intermediates 5ae5c failed.
1
PMe
Cl
Table 1
Cl
Cl
Cl
Co
N
Me P
Selected Spectroscopic Data of Complexes 7e10.
N
2 Co(PMe )
N
+
N
(2)
4
PMe
PMe
Cl
IR/cmꢀ1
Cl
Co
Cl
NMR/ppm
1H
Cl
Me P
31P
6
12
n
(C]N)
n(C]C)
r(PMe
3
)
PCH
3
CH]N
PMe
3
The reaction of diimine 6 with 2 equivalents of Co(PMe
3
)
4
in THF
7
8
9
1
1634, 1616
1647, 1613
1594
1591, 1569
1560, 1530
1568, 1542
1565, 1531
945
946
946
948
0.89
0.85
0.82
0.98
8.86, 8.16
9.05, 8.36
8.65
ꢀ26.1
ꢀ27.7
ꢀ26.6
ꢀ26.5
delivered double CeCl activation product, green dinuclear cobalt(II)
complex 12, via bis-ortho-metalation (Eq. (2)). The molecular
structure (Fig. 6) of complex 12 is closely related with that of the
corresponding dinuclear nickel(II) complex 9. The cobalt atoms
attain penta-coordinated tetragonal pyramids with the imine-N
atoms at the apical positions. Most of the structural parameters
of 12 are comparable with those of complex 9. The reaction of 6
0
1610
9.34
Fig. 3. Molecular structure of 8 (all the hydrogen atoms were omitted for clarity).
ꢀ
ꢁ
Selected bond distances (A) and angles ( ): Ni1eC7 1.882(3), Ni1eP1A 2.163(1), Ni1e
N1 2.187(3), Ni1eP2 2.197(1), Ni1eCl1 2.255(1); C7eNi1eP1A 91.5(1), C7eNi1eN1
8
Fig. 4. Molecular structure of 9 (all the hydrogen atoms were omitted for clarity).
ꢀ
ꢁ
Selected bond distances (A) and angles ( ): Ni1eC1 1.905(5), Ni1eN1 2.189(4), Ni1eP2
2.198(1), Ni1eP1 2.199(1), Ni1eCl1 2.273(2); C1eNi1eN1 82.6(2), C1eNi1eP2 89.7(1),
N1eNi1eP2 101.3(1), C1eNi1eP1 86.0(1), N1eNi1eP1 103.4(1), P2eNi1eP1 154.25(6),
C1eNi1eCl1178.2(2), N1eNi1eCl195.5(1), P2eNi1eCl190.66(6), P1eNi1eCl194.40(5).
2.0(1), P1AeNi1eN1 112.34(9), C7eNi1eP2 87.5(1) P1AeNi1eP2 144.13(6), N1eNi1e
P2 103.01(8), C7eNi1eCl1 177.3(1), P1AeNi1eCl1 86.69(5), N1eNi1eCl1 100.59(9),
P2eNi1eCl1 92.88(5), P1BeNi1eCl1 90.33(7).

118
J. Li et al. / Journal of Organometallic Chemistry 743 (2013) 114e122
Cl
Cl
B
N
Co
N
+2
Co(PMe3)
B
A
N
4
+
CoCl(PMe3)3
N
3
PMe3
A
A
Me P
PMe3
Cl
5
3
1
1
+
Co(PMe3)4
PMe3
+ 2
PMe3
3
N
A
Cl
N
Co
N
B
H
Co
Cl
N
B
Me P
3
Cl
5a
+
Co(PMe3)4
CoCl(PMe3)3
5c
N
2
PMe3
A
Co
N
PMe3
Me P
3
H
Cl
B
5b
3 4
Scheme 3. Reaction of 5 with Co(PMe ) .
products were formed in the reactions of aryl/alkyl chlorides
with Grignard reagents (entries 1e4, Table 2). It was found that
complex 11 is an efficient catalyst to the C,C-coupling reaction of
chlorobenzene with p-MeOC H MgBr (entry 5, Table 2). With a
6 4
catalyst loading of 1 mol%, 4-methoxybiphenyl could be isolated
in the yield of 50%. The reaction of complex 11 with the stoi-
chiometric amount of p-MeOC
6 4
H MgBr was investigated. After
stirring for 48 h a new signal was recorded at 1.4 ppm in the in
31
situ
P NMR spectra while the resonance of complex 11
at ꢀ12.2 ppm was also observed. Unfortunately, a try to isolate
the reaction products failed. It can be concluded that complex 11
is not stable in presence of Grignard reagent. This may also
explain why the yields are very poor for some of the substrates. A
systematic, deep and complete study on this catalytic system will
be in progress.
Fig. 5. Molecular structure of 11 (all the hydrogen atoms were omitted for clarity).
ꢀ
ꢁ
Selected bond distances (A) and angles ( ): Co1eN1 1.875(7), Co1eN2 1.965(6), Co1eP1
.184(3), Co1eP2 2.197(2), C6eCo1 1.930(8), N1eCo1eC6 80.8(4); N1eCo1eN2 85.7(3),
2
C6eCo1eN2 166.1(4), N1eCo1eP1 121.4(2), C6eCo1eP1 89.0(3), N2eCo1eP1 95.7(2),
N1eCo1eP2 113.1(2), C6eCo1eP2 88.4(3), N2eCo1eP2 99.7(2), P1eCo1eP2 124.1(1).
3 4
with 1 equivalent of Co(PMe ) also afforded complex 12. No mono-
nuclear cobalt complex as analog to mono-nuclear nickel(II) com-
plexes 7 and 8 could be obtained.
2.3. Bis-chelated complex 11 as catalyst in C,C-coupling reaction
1
mol % complex 11
Cl
+
BrMg
OMe
OMe (3)
THF, 40 C, 12h
50 %
Cl
N
catalyst:
Co
N
Me P
PMe
Fig. 6. Molecular structure of 12 (all the hydrogen atoms were omitted for clarity).
11
ꢀ
ꢁ
Selected bond distances (A) and angles ( ): Co1eN1 2.112(6), Co1eP2 2.305(4), Co1eP3
.317(4), C7eN1 1.31(1), Cl1eCo1 2.373(5), C14eN1 1.52(1); C1eCo1eN1 82.2(3), C1e
2
With bis-chelated complex 11 as catalyst the reactions of aryl/
alkyl chlorides with Grignard reagents were explored (Eq. (3)).
The experimental results showed that only trace cross-coupling
Co1eP2 86.9(2), N1eCo1eP2 100.0(2), C1eCo1eP3 89.8(2), N1eCo1eP3 97.6(2), P2e
Co1eP3 161.46(9), C1eCo1eCl11 77.6(2), N1eCo1eCl1 100.2(2), P2eCo1eCl1 92.7(1),
P3eCo1eCl1 89.81(14).

J. Li et al. / Journal of Organometallic Chemistry 743 (2013) 114e122
119
Table 2
Cobalt-catalyzed cross-coupling of aryl/alkyl chlorides with Grignard reagents.
Entry
ArCl
ArMgX
Product
Yield (%)
1
OMe
MgBr
Trace
Trace
Cl
OMe
MgCl
2
3
Cl
Cl
MgBr
Trace
4
5
Cl
MgBr
Trace
50
Cl
OMe
MgBr
OMe
3
. Conclusions
4.2. Synthesis of 3
In summary, the reactions of ortho-chlorinated compounds
bearing imine as anchoring groups with Ni(PMe and Co(PMe
A solution of compound 1 (0.68 g, 2.45 mmol) was added to the
ꢁ
3
)
4
3
)
4
solution of Ni(PMe
3
)
4
(0.89 g, 2.45 mmol) in THF (30 mL) at ꢀ80 C.
ꢁ
were investigated. By activation of the CeCl bonds novel ortho-
chelated nickel(II) and cobalt(II) complexes were obtained and
characterized. The dinuclear complexes Ni(II) and Co(II) com-
plexes were also isolated by oxidative addition of two aromatic
CeCl bonds. The CeCl cleavage product cobalt(I) 11 was formed
This mixture was allowed to warm to 20 C and stirred for 30 h to
form a redebrown turbid mixture. The volatiles were transferred
under vacuum, and the residue was extracted with diethyl ether
ꢁ
(40 mL). Crystallization from pentane at 4 C afforded yellow single
crystals of 3 (0.67 g, 56.2%) suitable for X-ray analysis. Analysis for 3,
through the reaction of diimine 5 with Co(PMe
3
)
4
. The proposed
C
20
H
28Cl
2
N
2
NiP
2
(487.97 g/mol), [found (calcd)]: C, 49.50 (49.22);
ꢀ1
mechanism of formation of complexes 11 was discussed. The
structures of complexes 3, 4, 8, 9, 11 and 12 were determined by
X-ray diffraction. With complex 11 as catalyst the reaction of
chlorobenzene with Grignard reagents was explored. It was found
that complex 11 is an efficient catalyst for the C,C-coupling re-
H, 5.52 (5.78); N, 5.60 (5.74). IR (Nujol mull, cm ): 1606
n
(C]N),
0.80 (t,
3
), 10.63 (s, 1H, CH]N), 8.87 (s, 1H,
1
941
3 6 6
n(PMe ). H NMR (300 MHz, C D , 297 K): d
2
4
j J(PH) þ J(PH)j ¼ 7.8 Hz, PCH
3
CH]N), 8.55, (m, 1H, AreH), 7.53 (d, 1H, J(HH) ¼ 7.2 Hz, AreH),
13
7.05 (m, 2H, AreH), 6.88 (m, 2H, AreH), 6.77 (m, 2H, AreH).
C
1
3
action of chlorobenzene and p-MeOC
6
H
4
MgBr. With a catalyst
NMR (75 MHz, C
6
D
6
, 297 K):
d
13.3 (t, j J(PC) þ J(PC)j ¼ 26.25 Hz,
loading of 1 mol%, 4-methoxybiphenyl could be isolated in the
yield of 50%.
PCH
3
), 161.6 (s, CH]N), 166.3 (s, CH]N), 121.6e140.5 (s, Carom).
3
1
ꢁ
P NMR (121 MHz, C
6
D
6
, 295 K):
d
ꢀ5.5 (s, PCH
3
). Dec. >110 C.
4.3. Synthesis of 4
4
. Experimental
A solution of compound 2 (1.14 g, 3.31 mmol) was added to the
4
.1. General procedures and materials
solution of Ni(PMe
3
)
4
(1.14 g, 3.31 mmol) in diethyl ether (30 mL)
ꢁ
ꢁ
at ꢀ80 C. This mixture was allowed to warm to 20 C and stirred
for 24 h to form a redebrown turbid mixture. The volatiles were
transferred under vacuum, and the residue was extracted with
Standard vacuum techniques were used in manipulations of
volatile and air-sensitive materials. Solvents were dried by known
procedures and distilled under nitrogen before use. Literature
ꢁ
pentane (40 mL). Crystallization from pentane at 4 C afforded dark
methods were used in the preparation of Ni(PMe
3
)
4
[38] and
red single crystals of 4 (1.0 g, 62.1%) suitable for X-ray analysis.
Co(PMe [39]. Schiff bases were obtained by condensation of 2-
chlorobenzenzaldehyde or 2,6-dichlorobenzenzaldehyde with
3
)
4
Analysis for 4, C20
42.98 (43.14); H, 4.90 (4.71); N, 4.89 (5.03). IR (Nujol mull, cm ):
4 2 2
H26Cl N NiP (556.88 g/mol), [found (calcd)]: C,
ꢀ
1
1
azide or ethylenediamine by refluxing in alcohol solution. Infrared
1605,
n
(C]N), 944
n
(PMe
3
). H NMR (300 MHz, C
6 6
D , 297 K): d 0.72
ꢀ1
2
4
spectra (4000e400 cm ), as obtained from Nujol mulls between
(t, j J(PH) þ J(PH)j ¼ 8.1 Hz, PCH
3
), 9.71 (s, 1H, CH]N), 10.41 (s, 1H,
1
13
31
3
KBr disks, were recorded on a Bruker ALPHA FT-IR. H, C and
P
CH]N), 7.32 (d, 1H, J(HH) ¼ 7.5 Hz, AreH), 6.88 (d, 2H,
3
3
NMR (300, 75 and 121 MHz, respectively) spectra were recorded on
J(HH) ¼ 7.5 Hz, AreH), 6.77 (d, 1H, J(HH) ¼ 8.4 Hz, AreH), 6.56 (t,
13
31
3
3
13
a Bruker Avance 300 spectrometer. C and P NMR resonances
were obtained with broadband proton decoupling. X-ray crystal-
lography was performed with a Bruker Smart 1000 diffractometer.
Elemental analyses were carried out on an Elementar Vario EL III.
Melting points were measured in capillaries sealed under nitrogen
and were uncorrected.
1H, J(HH) ¼ 7.5 Hz, AreH), 6.42 (t, 1H, J(HH) ¼ 8.1 Hz, AreH).
C
1
3
NMR (75 MHz, C
PCH ), 162.2 (s, CH]N), 164.4 (s, CH]N), 122.8 (s, Carom), 128.9 (d,
Carom), 130.4 (s, Carom), 135.7 (t, Carom), 132.1 (s, Carom), 135.7 (s,
6
D
6
, 297 K):
d
13.2 (t, j J(PC) þ J(PC)j ¼ 26.2 Hz,
3
31
Carom), ꢀ136.4 (m, Carom). P NMR (121 MHz, C
6 6
D , 295 K):
ꢁ
d
ꢀ19.1 (s, PCH
3
). Dec. >170 C.

120
J. Li et al. / Journal of Organometallic Chemistry 743 (2013) 114e122
4.4. Synthesis of 7
4.7. Synthesis of 10
A solution of compound 5 (0.37 g, 1.23 mmol) was added to the
A solution of compound 6 (0.4 g, 1.1 mmol) was added to the
ꢁ
ꢁ
solution of Ni(PMe
3
)
4
(0.44 g, 1.23 mmol) in THF (50 mL) at ꢀ80 C.
solution of Ni(PMe
3
)
4
(0.80 g, 2.2 mmol) in THF (50 mL) at ꢀ80 C.
ꢁ
ꢁ
This mixture was allowed to warm to 20 C and stirred for 24 h to
form a redebrown turbid mixture. The volatiles were transferred
under vacuum, and the residue was extracted with pentane (20 mL)
and diethyl ether (40 mL), respectively. Crystallization from pentane
This mixture was allowed to warm to 20 C and stirred for 24 h to
form a redebrown turbid mixture. The volatiles were transferred
under vacuum, and the residue was extracted with pentane (20 mL)
and diethyl ether (40 mL), respectively. Crystallization from
ꢁ
ꢁ
and diethyl ether at 4 C afforded red single crystals of 7 (0.39 g,
pentane and diethyl ether at 4 C afforded red single crystals of 10
6
3%) suitable for X-ray analysis. Analysis for 7, C22H32Cl N NiP
2 2 2
(0.69 g, 79%) suitable for X-ray analysis. Analysis for 10,
(
5
n
516.05 g/mol) [found (calcd)]: C, 51. 00 (51.20); H, 6.40 (6.25); N,
C
28
H
48Cl
4
N
2
Ni
2
P
4
(575.79 g/mol), [found (calcd)]: C, 41.00 (42.26);
ꢀ1
ꢀ1
.40 (5.43); IR (Nujol mull, cm ): 1634, 1616
n
(C]N), 1591, 1569
, 298 K): 0.89 (s,18H,
), 8.86 (s, 1H, CH]N), 8.16 (s, 1H, CH]N), 8.19 (dd, 1H,
H, 5.80 (6.08); N, 3.42 (3.52). IR (Nujol mull, cm ): 1610
n
(C]N),
, 298 K):
), 6.67 (t, 2H,
j J(HH) þ J(HH)j ¼ 7.8 Hz, AreH), 6.90 (d, 2H, J(HH) ¼ 7.2 Hz, Are
1
1
(C]C), 945
n
(PMe
3
). H NMR (300 MHz, C
D
6 6
d
1565,1531
n
(C]C), 948
n(PMe
3 6 6
). H NMR (300 MHz, C D
PCH
3
d
3
0.98 (s, 36H, PCH
3
), 5.03 (s, 4H, CH
2
3
4
3
4
3
J(HH) ¼ 8.1 Hz, J(HH) ¼ 1.8 Hz, AreH), 7.26 (d, 1H, J(HH) ¼ 7.2 Hz,
3
4
3
13
AreH), 7.04 (dd, 1H, J(HH) ¼ 6.9 Hz, J(HH) ¼ 0.9 Hz, AreH), 6.98
H), 7.10 (d, 2H, J(HH) ¼ 7.2 Hz, AreH), 9.34 (s, 2H, CH]N). C NMR
(75 MHz, C , 297 K): 13.8 (s, PCH ), 60.9 (s, CH ), 122.1 (s,
Carom), 131.3 (s, Carom), 132.5 (s, Carom), 136.8 (s, Carom), 138.9 (s,
3
4
(
dd, 1H, J(HH) ¼ 5.7 Hz, J(HH) ¼ 1.2 Hz, AreH), 6.82 (m, 4H, AreH),
6
D
6
d
3
2
3
4
4
.37 (t, 2H, j J(HH) þ J(HH)j ¼ 5.7 Hz, CH
2
), 4.30 (t, 2H,
). C NMR (75 MHz, C , 297 K):
), 61.8 (s, CH ), 157.8 (s, CH]N), 165.8 (s,
3
4
13
31
j J(HH) þ J(HH)j ¼ 5.8 Hz CH
2
D
6 6
Carom), 163.6 (s, CH]N). P NMR (121 MHz, C
(s, PCH
6
D
6
, 295 K):
d
ꢀ26.5
ꢁ
d
13.7 (s, PCH ), 60.9 (s, CH
3
2
2
3
). Dec. >180 C.
CH]N), 121.0 (s, Carom), 126.7 (s, Carom), 128.4 (s, Carom), 129.6 (s,
Carom), 131.1 (s, Carom), 133.7 (s, Carom), 135.1 (s, Carom), 138.3 (s,
4.8. Synthesis of 11
31
Carom), 139.7 (s, Carom), 142.7 (s, Carom). P NMR (121 MHz, C
6 6
D ,
ꢁ
2
95 K):
d
3
ꢀ26.1 (s, PCH ). Dec. >98 C.
A solution of compound 5 (0.62 g, 2.06 mmol) was added to the
ꢁ
solution of Co(PMe
3
)
4
(1.40 g, 4.12 mmol) in THF (50 mL) at ꢀ80 C.
ꢁ
4.5. Synthesis of 8
This mixture was allowed to warm to 20 C and stirred for 24 h to
form a brownish yellow turbid mixture. The volatiles were trans-
ferred under vacuum, and the residue was extracted with pentane
(20 mL) and diethyl ether (40 mL), respectively. Crystallization from
A solution of compound 6 (0.82 g, 2.2 mmol) was added to the
ꢁ
solution of Ni(PMe
3
)
4
(0.80 g, 2.2 mmol) in THF (50 mL) at ꢀ80 C.
ꢁ
ꢁ
This mixture was allowed to warm to 20 C and stirred for 24 h to
form a redebrown turbid mixture. The volatiles were transferred
under vacuum, and the residue was extracted with pentane (20 mL)
and diethyl ether (40 mL), respectively. Crystallization from
pentaneat 4 C afforded red singlecrystals of 11 (0.71 g, 72%) suitable
for X-ray analysis. Analysis for 11, C22
2 2
H32CoClN P (480.82 g/mol)
[found (calcd)]: C, 54.70 (54.95); H, 6.89 (6.71); N, 5.60 (5.83), IR
ꢀ1
1
(Nujol mull, cm ): 1637
, 298 K): 9.51 (s, 1H, CH]N), 8.46 (s, 1H, CH]N), 8.79 (s, 2H,
AreH), 7.78 (d, 1H, J(HH) ¼ 7.5 Hz, AreH), 7.18e7.33 (m, 5H, AreH),
3
n(C]N), 936 n(PMe ). H NMR (300 MHz,
ꢁ
pentane and diethyl ether at 4 C afforded red single crystals of 8
C
6
D
6
d
3
(
C
0.7 g, 60%) suitable for X-ray analysis. Analysis for 8,
NiP (584.93 g/mol), [found (calcd)]: C, 44.80 (45.17);
H, 5.20 (5.17); N, 4.82 (4.79), IR (Nujol mull, cm ): 1647, 1613
3
22
H
30Cl
4
N
2
2
3.64 (t, 2H, J(HH) ¼ 5.7 Hz, CH
2
), 0.80 (s,18H, PCH
3 2
), 3.49 (s, 2H, CH ).
ꢀ1
13
n
(C]
). H NMR (300 MHz, C
0.85 (d, J(PH) ¼ 7.2 Hz, PCH ), 9.05 (s, 1H, CH]N), 8.36 (s,
H, CH]N), 7.0 (d, 1H, J(HH) ¼ 7.5 Hz, AreH), 6.80 (m, 3H, AreH),
C NMR (75 MHz, C
6
D
6
, 297 K): 17.0(s, PCH ),162.2 (s, CH]N), 53.2
d
3
1
31
N), 1560,1530
n
(C]C), 946
n
(PMe
3
6
D
6
,
(s, CH
2
),118.8e132 (s, Carom),145.5 (s, CH]N),159.0 (s, CH]N).
P
3
ꢁ
2
1
6
98 K):
d
3
NMR (121 MHz, C
6
D
6
, 295 K):
d
ꢀ12.2 (s, PCH
3
). Dec. >148 C.
3
3
4
.55 (t, 1H, j J(HH) þ J(HH)j ¼ 7.8 Hz, AreH), 6.34 (t, 1H,
4.9. Experimental evidences of intermediate 5c
3
4
13
j J(HH) þ J(HH)j ¼ 8.1 Hz, AreH). 5.01 (s, 4H, CH
75 MHz, C , 297 K): 13.7 (s, PCH ), 60.9 (s, CH ), 62.4 (s, CH
22.0 (s, Carom), 128.4 (s, Carom), 129.7 (s, Carom),134.7 (s, Carom),
2
). C NMR
(
1
1
(
6
D
6
d
3
2
2
),
(a) IR monitoring: A solution of compound 5 (0.62 g, 2.06 mmol)
was added to the solution of Co(PMe
3
)
4
(1.40 g, 4.12 mmol) in THF
31
ꢁ
ꢁ
36.8 (s, Carom), 156.9 (s, CH]N), 163.9 (s, CH]N), P NMR
(50 mL) at ꢀ80 C. This mixture was allowed to warm to 20 C and
stirred for 10 h to form a green, turbid mixture.10 mL of the reaction
mother solution was sampled. The volatiles were removed under
vacuum. The solid residue was used for the FTIR analysis. Avibration
ꢁ
3
). Dec. >132 C.
121 MHz, C
6
D
6
, 295 K):
d
ꢀ27.7 (s, PCH
4.6. Synthesis of 9
-
1
at 1730 cm was found to be the signal of CoeH bond of interme-
1
A solution of compound 5 (0.37 g, 1.23 mmol) was added to the
diate 5c. (b) In situ H NMR: The sample of compound 5 (0.020 g,
0.065 mmol) was added in a solution of 0.6 mL of C
ꢁ
solution of Ni(PMe
)
3 4
(0.90 g, 2.47 mmol) in THF (50 mL) at ꢀ80 C.
6
D
6
with
ꢁ
ꢁ
This mixture was allowed to warm to 20 C and stirred for 24 h to
form a redebrown turbid mixture. The volatiles were transferred
under vacuum, and the residue was extracted with pentane (20 mL)
and diethyl ether (40 mL), respectively. Crystallization from pentane
Co(PMe
3
)
4
(0.024 g, 0.065 mmol) in a NMR tube at ꢀ80 C. This
mixture was allowed to warm to ambient temperature and stirred
1
6 6
for 10 h to form a green, turbid mixture. The in situ H NMR in C D
indicates clearlythe presence ofCoeH groupofintermediate5cwith
the hydrido resonance at ꢀ17.0 ppm as a broad peak.
ꢁ
and diethyl ether at 4 C afforded red single crystals of 9 (0.42 g,
6
2 2 2 4
6%) suitable for X-ray analysis. Analysis for 9, C28H50Cl N Ni P
(
3
526.90 g/mol) [found (calcd)]: C, 46.11 (46.27); H, 6.80 (6.93); N,
4.10. Synthesis of 12
ꢀ1
1
.84 (3.85); IR (Nujol mull, cm ): 1594
n
(C]N), 946
n
(PMe
3
). H
2
4
NMR (300 MHz, C
PCH
6
D
6
, 298 K):
d
0.82 (t, j J(PH) þ J(PH)j ¼ 8.1 Hz,
A solution of compound 6 (0.41 g, 1.1 mmol) was added to the
3
ꢁ
3
), 8.65 (s, 2H, CH]N), 7.22 (d, 2H, J(HH) ¼ 7.5 Hz, AreH), 6.97
solution of Co(PMe
3
)
4
(0.82 g, 2.25 mmol) in THF (50 mL) at ꢀ80 C.
3
4
ꢁ
(
dd, 2H, J(HH) ¼ 7.5 Hz, J(HH) ¼ 1.5 Hz, AreH), 6.87 (dt, 2H,
This mixture was allowed to warm to 20 C and stirred for 24 h to
form a redebrown turbid mixture. The volatiles were transferred
under vacuum, and the residue was extracted with pentane (20 mL)
and diethyl ether (40 mL), respectively. Crystallization from pentane
3
3
4
J(HH)
¼
7.2 Hz, J(HH)
¼
1.5 Hz, AreH), 6.80 (dd, 2H,
4
). 31P NMR
J(HH) ¼ 7.5 Hz, J(HH) ¼ 1.2 Hz, AreH), 4.91 (s, 4H, CH
2
ꢁ
(
121 MHz, C
6 6
D , 295 K):
d
ꢀ26.6 (s, PCH
3
). Dec. >198 C.

J. Li et al. / Journal of Organometallic Chemistry 743 (2013) 114e122
121
Table 3
Crystallographic data for complexes 3, 4, 8, 9, 11 and 12.
3
4
8
9
11
12
Empirical formula
Fw
Cryst syst
C
20
H
28Cl
2
N
2
NiP
2
C
20
H
26Cl
4
N
2
NiP
2
C
22
H
30Cl
4
N
2
NiP
2
C
28
H
50Cl
2
2
N Ni
2
P
4
C
22
H
32ClCoN
2
P
2
C
28
H
48Cl
4 2 2 4
Co N P
487.97
Monoclinic
C/2c
29.266(6)
9.0340(18)
20.890(4)
90.00
122.07(3)
90.00
556.88
584.93
726.90
480.82
Monoclinic
P2(1)/n
10.632(5)
14.025(7)
17.145(8)
90.00
104.765(7)
90.00
2472(2)
4
796.22
Orthorhombic
P2(1)2(1)2(1)
11.119(2)
13.343(3)
16.272(3)
90.00
90.00
90.00
2414.1(8)
4
1.532
Monoclinic
P2(1)/c
15.657(3)
8.5131(17)
21.221(4)
90.00
103.29(3)
90.00
2752.7(9)
4
Monoclinic
P2(1)/c
10.132(2)
9.2847(19)
19.179(4)
90.00
96.00(3)
90.00
1794.3(6)
2
Monoclinic
P2(1)/c
10.86(2)
9.89(2)
20.13(4)
90.00
100.92(4)
90.00
2123(7)
2
Space group
ꢀ
a, A
ꢀ
b, A
ꢀ
c, A
a
, deg
, deg
b
g
, deg
ꢀ
3
V, A
4679.9(16)
8
1.385
Z
ꢀ
3
Dc, g cm
1.411
1.345
1.292
1.245
No. of rflns collec.
No. of indep rflns
16320
5109
19710
5284
11630
4847
6339
3572
10276
3554
7235
2789
R
q
int
max, deg
R1 (I > 2
wR2 (all data)
0.0295
27.08
0.0349
0.2270
0.0365
27.13
0.0296
0.0824
0.0484
25.60
0.0503
0.1594
0.0551
26.73
0.0509
0.1011
0.0243
23.26
0.0949
0.2719
0.0727
22.63
0.0910
0.2715
s
(I))
ꢁ
and diethyl ether at 4 C afforded red single crystals of 12 (0.4 g, 64%)
suitable for X-ray analysis. Analysis for 12, C28 Co
796.22 g/mol), [found (calcd)]: C, 42.00 (42.23); H, 6.23 (6.08); N,
References
H48Cl
4
2 2 4
N P
[
[
[
1] V.V. Grushin, H. Alper, Chem. Rev. 94 (1994) 1047e1062.
(
2] T. Yamamoto, M. Nishiyama, Y. Koie, Tetrahedron Lett. 39 (1998) 2367e2370.
3] (a) M. Kawatsura, J.F. Hartwig, J. Am. Chem. Soc. 121 (1999) 1473e1478;
(b) M.W. Hooper, J.F. Hartwig, Organometallics 22 (2003) 3394e3404;
ꢀ1
3
.46 (3.52). IR (Nujol mull, cm ): 1680, 1637
n(C]N), 947
3
n(PMe ).
ꢁ
Dec. >172 C.
(c)M.W. Hooper, M. Utsunomiya, J.F. Hartwig, J.Org. Chem. 68(2003)2861e2873.
[
[
4] (a) A.F. Littke, G.C. Fu, Angew. Chem. Int. Ed. 37 (1998) 3387e3388;
(
(
b) A.F. Littke, G.C. Fu, Angew. Chem. Int. Ed. 38 (1999) 2411e2413;
c) A.F. Littke, C. Dai, G.C. Fu, J. Am. Chem. Soc. 122 (2000) 4020e4028.
4
.11. X-ray structure determinations
5] (a) A. Aranyos, D.W. Old, A. Kiyomori, J.P. Wolfe, J.P. Sadighi, S.L. Buchwald,
J. Am. Chem. Soc. 121 (1999) 4369e4378;
Intensity data were collected on a Bruker SMART diffractometer
ꢀ
(b) J.P. Wolfe, R.A. Singer, B.H. Yang, S.L. Buchwald, J. Am. Chem. Soc. 121
with graphite-monochromated Mo-K
a
radiation (
l
¼ 0.71073 A).
(
(
(
1999) 9550e9561;
The crystallographic data for complexes 3, 4, 8, 9, 11 and 12 are
summarized in Table 3. The structures were solved by direct
methods and refined with the full-matrix least-squares method on
c) J.P. Wolfe, S.L. Buchwald, Angew. Chem. Int. Ed. 38 (1999) 2413e2416;
d) J. Yin, M.P. Rainka, X.-X. Zhang, S.L. Buchwald, J. Am. Chem. Soc. 124 (2002)
1162e1163;
2
(e) X. Huang, K.W. Anderson, D. Zim, L. Jiang, A. Klapars, S.L. Buchwald, J. Am.
Chem. Soc. 125 (2003) 6653e6655;
all F (SHELXL-97) with non-hydrogen atoms anisotropic.
(
4
(
f) S.D. Walker, T.E. Barder, J.R. Martinelli, S.L. Buchwald, Angew. Chem. Int. Ed.
3 (2004) 1871e1876;
g) A.K. De Lewis, S. Caddick, F.G.N. Cloke, N.C. Billingham, P.B. Hitchcock,
J. Leonard, J. Am. Chem. Soc. 125 (2003) 10066e10073;
h) O. Navarro, R.A. Kelly III., S.P. Nolan, J. Am. Chem. Soc. 125 (2003) 11818e
1819.
4.12. Catalytic study
(
1
To a combination of complex 11 (3.4 mg, 0.007 mmol) and
chlorobenzene (80 mg, 0.71 mmol) in 3.0 mL of THF was slowly
added a solution of Grignard reagent 4-methoxyphenylmagnesium
[
[
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ꢁ
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2
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2326;
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3
4
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6
þ
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We gratefully acknowledge the support by NSF China No.
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