Crystal structures of benzoxazolyl-copper(iii,ii,i) complexes and investigation of Cu(ii)-mediated aryl carbon-hydrogen bromination

Article abstract of DOI:10.1039/c5dt01090j

Copper complexes have been frequently involved in many Cu-mediated carbon-hydrogen halogenation reactions. We fortunately obtained three different valence benzoxazolyl-copper complexes, along with aryl carbon-hydrogen bromination, in the self-assembly reaction of ligands with CuBr₂. The complexes have been successfully characterized by X-ray single crystal diffraction analyses. The results indicate that 1 consists of di-brominated p-benzoxazolylphenylamine (L) and an unusual high valence copper(iii) complex with tetrahedral geometry, 2 is the first polymeric catenulate di-brominated benzoxazolyl-copper(i) complex and 3 is the mono-brominated benzoxazolyl-copper(ii) complex. We speculate proposed mechanisms for the formation of these complexes and the bromination of aryl carbon-hydrogen based on these crystal structures. This journal is

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Crystal Structures of Benzoxazolyl-Copper(III, II, I) Complexes
and Cu(II)-Mediated Aryl Carbon-Hydrogen Bromination
Cite this: DOI: 10.1039/x0xx00000x
Lianke Wang, Hongping Zhou*, Jieying Wu, Yupeng Tian
Copper complexes have been frequently invoked in many Cu-mediated carbon-hydrogen halogenation
reactions. We fortunately obtained three different valents benzoxazolyl-copper complexes along with
the aryl carbon-hydrogen bromination in the self-assembly of ligands with CuBr2, which have been
Received 00th January 2012,
Accepted 00th January 2012
DOI: 10.1039/x0xx00000x
characterized by X-ray single crystal diffraction successfully. The results indicate that
brominated p-benzoxazolylphenylamine ( ) and the relevant unusual high valent copper(III) complexes
with tetrahedral geometries, is also the first polymeric catenulate di-brominated benzoxazolyl-
copper(I) complex and is the mono-brominated benzoxazolyl-copper(II) complex. We speculate the
1 consists of di-
L
www.rsc.org/
2
3
proposed mechanisms for the formation of these complexes and the bromination of aryl carbon-
hydrogen based on these crystal structures.
(III) complexes with tetrahedral geometries have been
reported in the literature.[1,3,4,7-11,17-19]
In the self-assembly of benzoxazolyl ligands with CuBr2 in
room temperature, we obtained three different valent ben-
zoxazolyl-copper complexes based on the mono-/di-
Introduction
In recent years, the earth-abundant copper salts have been
used as succedaneums of noble metals such as palladium to
mediate and catalyze carbon-hydrogen functionalization
reactions for constructing the formation of carbon-carbon and
carbon-heteroatom bonds.[1-6] In recent Cu-mediated/
catalyzed carbon-hydrogen activation reactions, researchers
speculated some proposed reaction mechanisms for the
formation of carbon-carbon and carbon-heteroatom bonds.[3,7-
brominated ligand
single crystal diffraction analysis. Herein, we present the
unprecedental example of benzoxazolyl-copper(III) complex
with tetrahedral geometries for the first time. At the same
time, also exhibits an unusual polemeric benzoxazolyl-
copper(I) chain. The structures also indicate that the Schiff
L that have been characterized by X-ray
1
2
11]
Among these mechanisms, the species of unusually high
base L1 and L2 were decomposed into L under the weak
acidity of Lewis Cu2+. In addition, we speculate the proposed
mechanism of Cu(II)-mediated direct aryl carbon hydrogen
valent Cu (III) are frequently suggested as an essential and key
intermediate that can urge the transformations of carbon-
hydrogen bond.[1,3,5,9,11,] The Cu (I) and Cu (II) is the most
common oxidation states, while the Cu (III) are scarce in
inorganic and coordination chemistry.
halogenation according to the crystal structures of
molecular structures of ligands L1 L2 and the brominated
products W1 W2 are shown in Scheme 1.
1-3. The
L
,
,
,
Since Burton et al reported the first crystallo-graphically
characterized copper(III) complex, [CuIII(CF3)2(SC(S)NEt2)] in
1989,[12,13] a few copper(III) complexes have been structurally
well-defined by rapid-injection nuclear magnetic resonance
(RI-NMR) spectroscopy, X-ray crystallography, X-ray absorption
spectroscopy (XAS) and et al successively.[1,5,10] Most Cu (III)
complexes show square-planar or tetrahedral geometries, in
agreement with a d8 electronic configuration. Thus the
strategy of using anionic tetradentate ligands to force square-
planar geometry has been widely used for stabilizing Cu (III)
complexes.[14,15] Similarly, porphyrins and corrole derivatives
have also been used to stabilize copper in high oxidation
state.[5,16,17]
Scheme 1 The molecular structures of ligand
brominated products W1 W2
L, L1, L2 and the
,
.
Results and discussion
Three copper complexes with different oxidation states are
stable under atmospheric conditions and their molecular
structures were determined based on X-ray single crystal
Although the formation of Cu (III) species has been fre-
quently suggested in recent Cu-mediated/catalyzed carbon-
hydrogen functionalization reactions, owing to the rather
reactive nature of Cu (III) species, they all cannot provide the diffraction analyses. The crystallographic data of
direct evidence to support their hypothesis.[18] Furthermore, to
the best of our knowledge, no structurally well-defined copper
1-3 are
summarized in Table 1, the selected bond lengths and angles
data and the geometrical parameters of the hydrogen bonds
are tabulated in Table S1-S2, ESI†), respectively.
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Table 1 Crystallographic data for 1-3.
1
2
3
empirical formula
C26H16Br7CuN4O2 C13H8Br3CuN2O C26H18Br4CuN4O2
formula weight
1039.34
Monoclinic
P 21/c
511.48
Monoclinic
P n
801.62
Triclinic
P -1
crystal system
space group
a [Å]
7.402(5)
21.994(5)
19.692(5)
90.000(5)
100.110(5)
90.000(5)
3156(2)
4
4.043(5)
14.545(5)
12.082(5)
90.000(5)
95.877(5)
90.000(5)
706.8(10)
2
7.974(5)
9.060(5)
9.663(5)
81.395(5)
73.778(5)
83.536(5)
660.9(6)
1
b [Å]
c [Å]
α [°]
β [°]
γ [°]
V [Å3]
Z
T [K]
296(2)
296(2)
296(2)
2.014
Dcalcd[g ·cm-3
μ [mm-1]
]
2.187
2.403
Fig. 2 (a) The two dimensional layer structure of
1
1, (b) the two
dimensional layer structure of , The colorized dotted lines
9.586
10.019
2.20-24.98
4840
6.905
represent the weak interactions and hydrogen atoms not
participating in hydrogen bonds are omitted for clarity.
θ range [°]
1.85-25.00
22266
2.21-25.00
4738
total no. data
no.unique data
no. params
R1
As shown in Fig. 2b (ESI†), the bromine atoms of the W2-
CuBr3 complex molecules form hydrogen bond interactions
with hydrogen atoms (H2B···Br1 2.732(1) Å, H2A···Br2 2.8252 Å,
H5···Br1 2.825(1) Å), yielding an infinite two dimensional layer
supramolecular structures in the solid state. The resulting
layers and W2 molecules are packed together to generate a
multilayer band structure by intermolecular weak interactions
between them, including H4B···Br3 2.909(1) Å, Br4···Br6 3.645
Å, Br3···N3 3.286 Å (Fig. 2a, ESI†), which indicate that the W2
5555
2349
2309
361
178
169
0.0476
0.1558
1.048
0.0232
0.0490
0.991
0.0618
0.1850
1.034
wR2
GOF
ligand is in favour of the crystallization process of 1. Fig. S1
(ESI†) exhibits the three dimensional latticed structure of
along the [100] direction.
1
Fig. 1 Molecular structure of 1. All hydrogen atoms are omitted for
clarity.
Fig. 3 (a) The molecular structure of unit of 2. (b) The one
dimensional polymeric chain of 2 formed by multiple Br-Cu-Br
bonds and π···π interactions. All hydrogen atoms are omitted for
clarity.
Structure of Benzoxazolyl-Copper(III) Complexes (1). The
crystal structure of complex 1 is illustrated in Fig. 1. Black complex 1
crystalizes in a monoclinic system and space group P21/c and the
asymmetric unit consists of two kinds of compounds: the dibromine
substituted p-benzoxazolyl-phenylamine (W2) and its copper
complex (W2-CuBr3). The bromine atoms substitute the o-positions
of phenylamine. In addition, the copper atom is four-coordinated
and displays a seriously distorted tetrahedral geometry supplied by
three bromine atoms (Cu1-Br1 2.3397(15) Å, Cu1-Br2 2.3707(19) Å,
Cu1-Br3 2.4202 Å, Br1-Cu1-Br2 96.91(6) °, Br1-Cu1-Br3 96.17(7) °,
Br2-Cu1-Br3 146.41(7) °) and one nitrogen atom from benzoxazole
group (Cu1-N1 1.997(6) Å, N1-Cu1-Br1 151.3(2)°, N1-Cu1-Br2
92.05(19)°, N1-Cu1-Br3 91.1(2)°). These bond lengths and angles
around copper center are analogous to that of other copper
complex systems.[33-37] The existence of the neutral W2 compounds
and the three bromine atoms in 1 clearly indicates that the copper
center is in high-valent +3 oxidation states. Thus, 1 presents the
first unusual high-valent copper(III) complex with tetrahedral
geometry. [1,3,4,7-11,17-19]
Structure of Benzoxazolyl-Copper(I) Complexes (2). X-ray single
crystal diffraction analysis reveals that
2 crystallizes in the
monoclinic system with space group P n and the crystal structure of
unit is depicted in Fig. 3a. Fig. 3b shows that 2 features one
dimensional polymeric chains formed by multiple Br-Cu-Br bonds
(Br1-Cu1 2.411(2) Å, Br1-Cu1#2 2.392(2) Å) and π···π interactions (d
= 3.363 Å). In the structure of 2, the copper center is three-
coordinated by two Br atoms and one
N atom from the
benzoxazolyl group in a planar trigonal geometry, and the Br atoms
are also coordinated with two copper atoms, respectively (Fig. 3b).
To the best of our knowledge, 2 is the first three-coordinated
copper bromine coordination polymer with CuI-Br-CuI structural
motif that has been structurally characterized.[20-25] These one
dimensional polymeric chains are further linked to form three
dimensional supramolecular network architecture by multiple N-
H···Br (H2B···Br1 3.045(3) Å, H2A···Br3 2.888(1) Å), C-H···O (H3···O1
2.771(3) Å), Br···Br (Br2···Br3 3.497(4) Å) interactions, as shown in
2 | J. Name., 2012, 00, 1-3
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Fig. S2 (ESI†). It is no doubt for these existing intramolecular occupied by two nitrogen atoms from two benzoxazolyl groups and
hydrogen bonds to contribute significantly to the alignment of the two bromine atoms. The distance between copper center and
molecules in the crystalline state.
nitrogen atoms is 1.983(7) Å and the Cu-Br bond length is 2.4266(15)
Å. The angles of N-Cu-Br are 90.1(2)° and 89.9(2)°, respectively. Fig.
4b (ESI†) displays the one dimensional band structure of 3 formed
by the N-H···Br (H···Br 2.767(2) Å) hydrogen bonds.
Br
Br
O
O
CuBr2
L1 or L2
NH2
NH2
N
N
Br
Br
Cu(III)
Cu(II)
Br
Br
Br
Br
Br
Lewis Cu2+
CuBr2
Br
Br
Br
O
N
CuBr
NH2
O
N
O
N
CuBr2
NH2
NH2
n
Br
Cu(I)
W2
L
Br
Br
O
N
NH2
Br
O
N
O
N
CuBr2
CuBr2
NH2
Br Cu Br
N
NH2
L
W1
H2N
O
Br
Scheme 2 Proposed mechanisms for synthesis of benzoxzolyl-
copper complexes.
Formation of Benzoxazolyl-Copper Complexes. The above
results clearly demonstrate that the Schiff base ligands L1 and L2
decomposed into ligand L under the weak acidity of Lewis Cu(II).
And then, ligand L firstly transforms into new ligand W1 or W2
through the carbon-hydrogen bromination of aniline, which can be
proved by the above crystal structures. The resulting ligand W2
coordinates with CuBr2 to produce the intermediate W2-CuBr2. The
Cu(II) ion acts as an oxidant to oxidize the intermediate W2-CuBr2
into complex W2-CuBr3, and itself is reduced into Cu(I) ion. Finally,
the complex W2-CuBr3 crystallizes with ligand W2 to produce 1. On
the other hand, the resulting CuBr coordinates with ligand W2 to
produce polymeric 2. The direct coordination between the mono-
brominated W1 with CuBr2 produces complex 3, which may restrict
the further bromination of W1 and the oxidation of copper(II)
complex. The stepwise formation of these benzoxazolyl-copper
complexes are shown in Scheme 2.
Fig. 4 (a) Molecular structure of 3. (b) The one dimensional chain
structure of 3 formed by multiple N-H···Br interactions. The
colorized dotted lines represent the weak interactions and
hydrogen atoms not participating in hydrogen bonds are omitted
for clarity. All hydrogen atoms are omitted for clarity.
Structure of Benzoxazolyl-Copper(II) Complexes (3). Fig. 4a
exhibits the molecular structure of complex 3. X-ray single crystal
diffraction analysis demonstrates that complex 3 crystalizes in a
triclinic system, space group P-1. Different from complex 1 and 2,
complex 3 performs a symmetric unit that consists of one
independent Cu atom, two coordinated bromine groups and two
mono-bromine substituted p-benzoxazolylphenylamines (W1).
Obviously, the copper center is four-coordinated in square-planar
geometry and the equatorial positions of copper center are
Br
N
O
N
N
O
NH2
NH2
NH2
O
Br
Br
L
W2
W1
CuBr2
Br-
CuBr2
Br Br
Cu(II)
N
O
N
O
N
O
N
O
NH2
NH2
NH2
Br
NH2
Cu(II)
Br
K
Br
F
A
E
CuBr2
Br-
Br
Cu(I)
CuBr2
CuBr2
CuBr2
Br
Br
Cu(I)
Br
Br
Cu(III)
Cu(III)
N
O
N
O
N
O
N
O
NH2
NH2
NH2
NH2
Cu(III)
Br
Cu(III)
Br
Br
Br
B
D
J
G
Br
Br
Br
Br
Br
H
-H+
Cu(III)
NH2
-H+
N
N
O
NH2
O
C
Cu(III)
Br
H
H
Br
Scheme 3 Proposed mechanisms for the Cu-mediated carbon-hydrogen bromination of aniline.
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Bromination Mechanism of Aryl Carbon Hydrogen. On the
Conclusions
basis of the above depicted works and the related
literatures[3,5,11,17,18,26-29], we speculated and proposed a 2Cu(II)
→Cu(III) + Cu(I) mechanism for the brominaꢀon reacꢀons, as
shown in Scheme 3. Namely, coordination of Cu(II) with amino
In summary, we have reported for the first time the crystal
structures of a series of stable benzoxazolyl-copper complexes with
three different oxidation valent states (+3, +2 and +1). To the best
of our knowledge, 1 presents the unprecedented high-valent
benzoxazolyl-copper(III) complex with tetrahedral geometry, 2 is
also the first example of benzoxazolyl-copper(I) complex that
contains polymeric CuI-Br-CuI structural chain and 3 is mono-
brominated benzoxazolyl-copper(II) complex. According to these
crystal structures, we speculate the possible bromination process of
aryl carbon-hydrogen and the formation of these benzoxazolyl-
copper complexes.
group in
transfers to the high valent Cu(III) intermediate
oxidation of CuBr2, and the CuBr2 simultaneously translates
into CuBr.[5,11,18,26] Here, the above mentioned complex
and
L
generates the Cu(II) intermediate
A
. Intermediate
A
B
under the
1
2
can provide the direct evidence to support the existence of
Cu(III) and Cu(I) in the system. And then, nucleophilic attack of
the phenyl ring to highly valent Cu(III) center in the
intermediate
intermediate
B
produces the Cu(III) intermediate
through dearomatization
D
via
and
C
a
rearomatization process.[3,18] Finally, the reductive elimination
Experimental
of intermediate
nucleophilic attack of the bromine ions to active intermediate
delivers the mono-brominated product W1. At this point,
transfers to W1 through the above the transformation of
intermediates. Then, W1 gets into the next same catalytic
cycle process to produce the di-brominated product W2
D generates the intermediate E and the
Materials and methods. All commercially available chemicals
and solvents are of reagent grade and were used as received
without further purification. Theoretical calculations were carried
out using Gaussian 03W package of programs based on their
molecular conformation in the crystal structure.
E
L
Crystal Structure Determination. The X-ray diffraction
measurements were performed on a Bruker SMART CCD area
through the transformation of intermediates F, G, H, J and K.
The existences of mono-/ di-brominated product W1 or W2 in
the complexes effectively prove that the above proposed
mechanisms of carbon-hydrogen bromination of aniline are
reasonable.
Table 2 The Mulliken charge distribution of N atoms in
different ligands
detector using graphite monochromated MoK radiation (λ
=
0.71069 Å) at 298 (2) K. Intensity data were collected in the variable
ω-scan mode. The structures were solved by direct methods and
difference Fourier syntheses. The non-hydrogen atoms were
refined anisotropically and hydrogen atoms were introduced
geometrically. Calculations were performed with SHELXTL-97
program package. Crystallographic data (excluding structure factors)
for the structures reported in this paper have been deposited with
the Cambridge Crystallographic Data Centre as supplementary
publication no. CCDC: 1020489, 1020490, 1038362.
Ligands
qN1
L
W1
W2
-0.555
-0.730
-0.574
-0.721
-0.595
-0.707
qN2
qN1: the Mulliken charge of N atom in benzoxazolyl group, qN2: the
Synthetic procedures. The ligands were prepared according to
the synthetic routes shown in Scheme S1 (ESI†) and our previous
work [32]. Complexes 1-3 were prepared by a similar procedure. The
methanol solution (20 mL) of CuBr2 (0.447 g, 2 mmol) were added
into the solution of ligands (L1: 0.314 g, 1 mmol, L2: 0.401 g, 1
mmol and L: 0.210 g, 1 mmol) in dichloromethane (10 mL) and the
product was obtained by slow interlayer diffusion at room
temperature, respectively. We single out the stable and regular
single crystals of 1-3 under microscope and the crystals are
characterized by single crystal X-ray diffraction analyses. Result: 1,
black block crystal, 0.075 g, yield 9.85%, 2, light yellow needle
crystal, 0.067 g, yield 7.9%, 3, black block crystal, 0.09 g, yield 13.3%.
Mulliken charge of N atom in amino group.
We calculated the Mulliken charge distribution of nitrogen
atoms in different ligands by using the density functional theory at
B3LYP/6-31G(d) level based on their molecular conformation in the
crystal structures, and the results are shown in Table 2 and Fig. S3-
S4 (ESI†).[30-31] The Mulliken charge of N atom in amino group is
more negative than that in benzoxazaolyl group, which illustrates
that the amino group is easier to coordinate with Cu(II) ion than
benzoxazaolyl group. With the increasing of bromine in ligand L, the
Mulliken charge of N atom in amino group decreases and however
the Mulliken charge of N atom in benzoxazolyl group increases. At
the same time, the existence of two bromines atoms enhances the
steric hindrance, which also effectively restrains the further
coordination between copper ions and amino group. These
discussions indicate that the nitrogen atoms in benzoxazaolyl group
are inclined to coordinate with copper ions. In addition, there not
exists the nucleophilic attack of the phenyl ring to Cu(III) center in
the product W2-CuBr3 in the formation of benzoxazolyl-copper(III)
complexes, which may be caused by the existence of bromine
atoms. The explanation can be generalized in two aspects: the
bromine atoms act as electron-withdrawing groups to reduce the
electronegativity of phenyl group and the bromine atoms also
increase the steric hindrance of phenyl group, which eliminate the
possibility of the nucleophilic attack of the phenyl ring.
Acknowledgements
This work was supported by the Program for New Century
Excellent Talents in University (China), the Doctoral Program
Foundation of the Ministry of Education of China
(20113401110004), the National Natural Science Foundation
of China (21271003, 21271004, 51472002 and 51432001), the
Natural Science Foundation of Education Committee of Anhui
Province (KJ2012A024), the 211 Project of Anhui University,
Higher Education Revitalization Plan Talent Project of (2013).
Notes and references
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DOI: 10.1039/C5DT01090J
We report three new copper complexes with different oxidation states based on phenylbenzoxazole system.
64x51mm (600 x 600 DPI)